聚合物反应注射成型

本文简要地介绍了反应注射成型(RIM)的发展,RIM的化学体系,RIM过程和制品的成型,RIM过程的主要特点及RIM聚氨酯的主要组分。     

ToF‐SIMS characterization of glyoxal surface oxidation products by hydrogen peroxide: A comparison between dry and liquid samples

As one of the simplest volatile organic compounds, glyoxal and its oxidation products were considered to be important precursors to aqueous secondary organic aerosol formation. Herein, we analyzed products from glyoxal oxidation by hydrogen peroxide in dry and liquid samples using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). ToF‐SIMS spectra and spectral principal component analysis (PCA) were used to investigate surface oxidation products. Dry samples were prepared on clean silicon wafers. Liquid samples consisting of glyoxal and hydrogen peroxide (H₂O₂) were introduced to a vacuum compatible microfluidic reactor prior to UV illumination or dark aging followed by in situ liquid SIMS analysis. A number of reaction products were observed in both dry and liquid samples; different oligomers and carboxylic acids could be formed depending on reaction conditions. In addition, hydrolyzed products were observed in the liquid samples, but not in the dry samples. Although dry samples reveal some products of the aqueous process, they are not fully representative as results from those of the aqueous samples. Our findings suggest that the ability to characterize the liquid surface reaction products provides more realistic information of the reaction products associated with aqueous secondary organic aerosol formation in the atmosphere. Meanwhile, the high mass resolution spectra from the dry sample SIMS measurement are helpful to identify oxidation products in the liquid samples.     

Cyclic oligomers content in anionic poly (ϵ-caprolactam)

The influence of initiator and activator concentrations on the anionic polymerization of ϵ-caprolactam and, in particular, on the methanol – extractable fraction of the final polymer has been widely studied. Due to the increasing interest of this polymerization in the field of reaction injection molding (RIM) technology, a thorough investigation has been also carried out to find the best experimental conditions for this reaction in the mold. The effect of postpolymerization annealing on the overall amount of low-molecular mass substances, among which cyclic oligomers, has been evaluated. Thermal properties as well as crystallinity of the resultant materials have been examined. A comparison with literature data is given; the suggested correlation between the amount of the oligomeric fraction and the molecular arrangement of the polymer in the solid state is discussed.     

Simultaneous determination of amantadine and rimantadine by HPLC in rat plasma with pre-column derivatization and fluorescence detection for pharmacokinetic studies

We investigated simultaneous high-performance liquid chromatographic (HPLC) determination of amantadine hydrochloride (AMA) and rimantadine hydrochloride (RIM) levels in rat plasma after fluorescent derivatization with o-phthalaldehyde and 2-mercaptoethanol. Afterwards, the method was applied to determine their pharmacokinetics. The retention times of AMA and RIM derivatives were 12.6 and 22.2 min and the lower limits of detection were 0.025 and 0.016 microg/mL, respectively. The coefficients of variation for intra- and inter-day assay of AMA and RIM were less than 5.1 and 7.6%, respectively. After i.v. administration of AMA or RIM to rats, the total body clearance and distribution volume at the steady-state of RIM were higher than those of AMA. Bioavailability of AMA and RIM was 34.9 and 37.2%, respectively. When AMA and RIM were p.o. co-administered, the area under the plasma concentration--time curve of RIM was significantly lower than that after RIM alone. On the other hand, pharmacokinetic parameters of AMA did not significantly change. These results indicate that our HPLC assay is simple, rapid, sensitive and reproducible for simultaneously determining AMA and RIM concentrations in rat plasma and is applicable to their pharmacokinetic studies. Also, co-administration of AMA and RIM may result in the lack of pharmacological effects of RIM.     

Nickel(Ⅱ) a-Diimine Catalysts with Carboxyl Groups for Ethylene Oligomerization and Polymerization

A series of nickel(II) ?-diimine complexes with strong electron-withdrawing carboxyl groups, having reactive hydrogen atoms, were prepared and used as precatalysts for ethylene oligomerization and/or polymerization. The influence of metal halides and ligand structure on the catalytic activity and properties of products was investigated. The results showed that nickel bromide was much more active than nickel chloride, and the substituents at the ortho-position of aryl ring had large influence on the properties of products. Therefore, the products ranging from liquid oligomers to polymers could be readily obtained by the variation of the substituents on the ligands and reaction conditions.     

MALDI-TOF characterization of macromonomers

Methacryloyl endfunctionalized oligostyrene macromonomers were characterized by matrix assisted laser desorption ionization/time of flight (MALDI-TOF) spectroscopy and by isocratic and gradient high performance liquid chromatography (HPLC). The molar mass distribution derived by the different techniques coincide for the investigated oligomers. Mixing experiments revealed that the MALDI-TOF peak areas do not necessarily represent the mixing ratio of the components. Combination of gradient HPLC and MALDI-TOF has resolved the chemical composition of the coupling products formed by reaction of the living anion with oxygen.     

Model reactions of amine curing of glycidylamine epoxy resins: Homopolymerization of N-methylglycidylaniline

The kinetics of homopolymerization of the monofunctional epoxide N-methylglycidylaniline in the presence of a tertiary amine or an amino alcohol has been followed by reversed phase high performance liquid chromatography and size exclusion chromatography. The reaction products were identified by mass spectrometry using potassium ionization of desorbed species (K⁺IDS). 1,3-Di-N-methylanilino-2-propanol (P) was the main reaction product and low molecular weight oligomers with M_n > 600 were also formed. The molecular weight and fraction of oligomers decrease with increasing concentration of the initiator. The suggested complex reaction mechanism involves formation of four stable oligomeric series initiated by reaction of the epoxide with either an OH group of (a) the amino alcohol, (b) product P, (c) traces of water, or (d) the tertiary amine to form ionic species resulting in the ionic propagation. Regeneration of the initiator and formation of new initiating centers during the polymerization are the causes of low molecular weights of oligomers. © 1992 John Wiley & Sons, Inc.     

Secondary organic aerosol formation during the photooxidation of toluene: NOx dependence of chemical composition

The photooxidation of toluene is a potential source of secondary organic aerosol (SOA) in urban air, but only a small portion of the compounds present in SOA have been identified. In this study, we analyzed the chemical compositions of SOA produced by photoirradiation of the toluene/NOx/air system in laboratory chamber experiments by a combination of liquid chromatography-mass spectrometry, hybrid high-performance liquid chromatography-mass spectrometry, and iodometry-spectrophotometry. The dependence of the chemical composition on the initial NOx concentration was examined at initial NO concentrations ([NO]0) of 0.2 and 1 ppmv. Fifteen semivolatile products, including aromatic and ring-cleavage compounds, were quantified. However, the quantified products comprised only a small portion ( approximately 1 wt %) of the total aerosol mass. The total SOA yield ( approximately 13 wt %), the ratio of organic peroxides to total SOA mass ( approximately 17 wt %), and the density of SOA ( approximately 1.4 g cm-3) were independent of the NOx level, suggesting that the reaction mechanisms of the formation of major SOA products at [NO]0 = 0.2 and 1 ppmv are essentially the same. The negative-ion mass spectra of SOA samples showed that ion signals attributed to hemiacetal oligomers and/or decomposition products of peroxy hemiacetal oligomers were detected in the range of mass-to-charge ratios (m/z) between 200 and 500. The highest signals were detected at m/z = 155 and 177, and these were tentatively assigned to C7 unsaturated oxacyclic oxocarboxylic acids and C7 unsaturated oxacyclic dicarboxylic acids, respectively. We conclude that the major chemical components of the aerosol are hemiacetal and peroxy hemiacetal oligomers and low-molecular-weight dicarboxylic acids.     

Synthesis and study of polymerization and copolymerization of some oligounsaturated esters—V

A number of oligoacetylenic acrylates have been synthesized and characterized. The i.r. as well as the physical and chemical properties show the probable formation of oligomers possessing a proposed structure. The oligomers undergo further reaction in the presence of peroxide initiators to give crosslinked products. The i.r. spectra of the crosslinked products show that the oligomers undergo addition polymerization on the terminal double bonds. The triple bond in these oligomers is relatively unreactive under the conditions of polymerization, while that in the glycolic residue is reactive to a certain extent, as indicated by the higher per cent conversion of the oligomers having such unsaturated glycolic residue.Copolymerization of various oligoacetylenic acrylates, methacrylates and esters with terminal allylic group with styrene give crosslinked products. The polymers and copolymers are pale yellow in colour, glassy, insoluble in organic solvents and infusible; the copolymers were more rigid than the homopolymers. The volume shrinkage of various oligomers during polymerization lies between 5 and 13 per cent.     

Elementosiloxane oligomers and their cross-linking by metal porphyrazines

Elementosiloxane oligomers were synthesized, and their properties and the reaction of cross-linking by metal porphyrazines, which are known to catalyze vulcanization of liquid low-molecular-weight elementosiloxane oligomers, were studied. The properties of the fireproof materials with vulcanized siloxane coatings based on the elementosiloxane oligomers modified with boron, aluminum, and titanium were examined. It was established that these materials have high physicomechanical and fireproofing properties.     

Biphasic oligomerization of ethylene with nickel complexes immobilized in organochloroaluminate ionic liquids

Ethylene was selectively oligomerized by nickel complexes such as (PPh₃)₂NiBr₂ and (PPh₃)₂NiCl₂ immobilized in chloroaluminate ionic liquid in biphasic catalytic reactions. The influence of reaction parameters such as reaction media, reaction temperature and Et₂AlCl:Ni molar ratio was also evaluated. Turnover frequency up to 24000 mol C₂H₄/(mol Ni h) was achieved under mild reaction conditions (0.5 atm and 40 °C). GC‐MS analyses showed that the obtained oligomers completely consist of C4 and C6. The olefinic products can be easily separated from the catalytic ionic liquid phase by simple decantation, and the nickel catalyst can be reused without a significant decrease in turnover frequency and change of the distribution of the olefinic products. Copyright © 2009 John Wiley & Sons, Ltd.     

Ring-opening metathesis phase-trafficking (ROMpt) synthesis: multistep synthesis on soluble ROM supports

The use of ring-opening metathesis (ROM) oligomers as soluble supports for a multistep reaction sequence is described. A Mitsunobu reaction followed by an in situ ROMP-mediated phase-trafficking purification is utilized to generate soluble ROM oligomers that are isolated via precipitation with methanol. Once formed, the ROM oligomers serve as soluble supports for further solution-phase reactions, including a ring-closing metathesis. After each step, the support-bound products are isolated by precipitation with a suitable solvent. [reaction--see text]     

Manufacture of xylose-based fermentation media from corncobs by posthydrolysis of autohydrolysis liquors

Milled corncob samples were mixed with water and heated to obtain a liquid phase containing oligosaccharides, sugars, and acetic acid as main reaction products (autohydrolysis reaction). To hydrolyze the sugar oligomers to the correspondent monomers, sulfuric acid was added to the autohydrolysis liquors to reach 0.5–2 wt% of solution, and the reaction media were heated at 101.5–135°C. With this operational procedure, sugar solutions suitable as fermentation media (containing xylose as the major component) were obtained. The kinetics of the posthydrolysis step was characterized on the basis of experimental data concerning the time courses of the concentrations of xylooligosaccharides, xylose, furfural, and acetic acid. The concentrations of other reaction byproducts (glucose or arabinose) were also measured.     

聚二甲基硅烷的热分解研究

聚二甲基硅烷的热分解研究宋永才，商瑶，冯春祥，陆逸（国防科技大学材料科学与应用化学系长沙４１００７３）关键词聚二甲基硅烷，热分解，热解产物，结构聚二甲基硅烷（ＰＤＭＳ）是以Ｓｉ－Ｓｉ键构成主链的聚合物．在惰性气氛中经热解重排可转化为以Ｓｔ—Ｃ键为骨架...     

Radiation yield of stable radiolysis products of 1-chlorobutane, 1-chlorobutene-2, 1-chloropropane, 2-chloropropane and 1,3-dichloropropane γ-irradiated in an oxygen-free atmosphere

The stable radiolysis products of 1-chlorobutane (1-CB), 1-chlorobutene-2 (1-CB-2), 1-chloropropane (1-CP), 2-chloropropane (2-CP) and 1,3-dichloropropane (1,3-DCP) gamma-irradiated in an oxygen-free atmosphere have been investigated. The pure radiolysis products were separated by preparative gas chromatography and identified by NMR and mass spectroscopy as well as qualitative gas chromatography. The compounds formed were determined by potentiometric analysis and quantitative gas chromatography. From 1-CB we have obtained in the gas phase: HCl, H₂, butane; in the liquid phase: 2-chlorobutane, 1,3-dichlorobutane and a mixture of oligomers of the initial compound (dimer and trimer). We have not recorded H₂ in 1-CB-2. The main gaseous products of radiolysis of 1-CP are HCl and H₂. Radiation yield of isomerization was determined. From 2-CP we have obtained in the gas phase: HCl and H₂; in the liquid phase: 2,2-dichloropropane and a mixture of oligomers of the initial compound (dimers and trimers). From 1,3-DCP we have found in the gas phase: HCl and H₂; in the liquid phase: 1-CP, 2-CP, 1,2-DCP and oligomers. Preliminary schemes for the formation of stable products are proposed.     

Simultaneous determination of the binding of amantadine and its analogues to synthetic melanin by liquid chromatography after precolumn derivatization with dansyl chloride

For the determination of amantadine (1-ADA), 2-adamantanamine (2-ADA), memantine (MEM), and rimantadine (RIM) in melanin binding studies, the simultaneous determination of 1-ADA or 2-ADA, MEM, and RIM is investigated by high-performance liquid chromatographic assay with dansyl chloride as a fluorescent derivative reagent. Dansyl derivatives with fluorescent intensity are detected at an excitation wavelength of 370 nm and an emission wavelength of 506 nm. Retention times of 1-ADA, 2-ADA, MEM, and RIM derivatives are 12.2, 12.2, 15.2, and 16.6 min, respectively. The peak of 1-ADA derivative coelutes with the 2-ADA derivative. The limits of detection for 1-ADA, 2-ADA, MEM, and RIM are 0.014, 0.007, 0.012, and 0.020microM, respectively (signal-to-noise ratio of 3:1). In the intra- and interday assay, the range of standard deviation to the average of 1-ADA, 2-ADA, MEM, and RIM is 4.6-12.7%. Their recovery is also good. The ranking order for synthetic melanin binding among these compounds is RIM > MEM > 2-ADA = 1-ADA. The method is simple, sensitive, and reproducible for simultaneously measuring 1-ADA or 2-ADA, MEM, and RIM. Also, it is useful to investigate their binding kinetics to melanin.     

聚双环戊二烯反应注射成型

本文介绍了国外有关聚双环戊二烯反应注射成型的研究进展，讨论了国内进行聚双环戊二烯反应注射成型开发研究的现实意义，并对这一领域的发展进行了展望     

Analysis of linear and cyclic oligomers in polyamide-6 without sample preparation by liquid chromatography using the sandwich injection method. II. Methods of detection and quantification and overall long-term performance

By separating the first six linear and cyclic oligomers of polyamide-6 on a reversed-phase high-performance liquid chromatographic system after sandwich injection, quantitative determination of these oligomers becomes feasible. Low-wavelength UV detection of the different oligomers and selective post-column reaction detection of the linear oligomers with o-phthalic dicarboxaldehyde (OPA) and 3-mercaptopropionic acid (3-MPA) are discussed. A general methodology for quantification of oligomers in polymers was developed. It is demonstrated that the empirically determined group-equivalent absorption coefficients and quench factors are a convenient way of quantifying linear and cyclic oligomers of nylon-6. The overall long-term performance of the method was studied by monitoring a reference sample and the calibration factors of the linear and cyclic oligomers.     

Cross-linking of borosiloxane oligomers and properties of materials with vulcanized borosiloxane coating

Cross-linking of liquid borosiloxane oligomers was studied. The reaction is described by a first-order rate equation for irreversible reactions. The effective cross-linking rate constants and activation energies of the reaction were calculated. The properties of materials with the vulcanized borosiloxane coating were studied. The physicomechanical properties of materials with borosiloxane coating are higher than those of materials with coatings based on vulcanized liquid siloxane rubbers.     

Reaction of (diacetoxyiodo)benzene with excess of trifluoromethanesulfonic acid. A convenient route to para-phenylene type hypervalent iodine oligomers

Reaction of (diacetoxyiodo)benzene [PhI(OAc)₂] in trifluoromethanesulfonic acid (TfOH) resulted in oligomerization of PhI(OAc)₂. Quenching with NaBr gave the bromide salts of hypervalent iodine oligomers that were determined by thermolysis with KI to be a para phenylene type of oligomers. Neutralization of the reaction mixture of PhI(OAc)₂ and TfOH with aqueous NaHCO₃ yielded the triflate salts of iodine oligomers. Furthermore, quenching the reaction mixture with aromatic substrates afforded arylated iodine oligomers. These iodine oligomers were found to be 3-4 of the number average degree of polymerization (P_n) by GC analysis of the thermolysis products and ¹H NMR analysis. The major products, trimer and tetramer, were synthesized independently.