One-pot synthesis and characterization of a new, branched polycarbosilane bearing allyl groups

A highly branched polycarbosilane bearing allyl groups has been prepared by a one-pot synthesis with chloromethyltrichlorosilane, chloromethylmethyldichlorosilane and allyl chloride as the starting materials. The resultant polymer, with the approximate formula [SiH1.2(CH3)0.71(CH2CHCH2)0.09CH2]n, has been characterized by 1H, 13C, and 29Si NMR, GPC, TG and elemental analysis. It could be cross-linked thermally at 170 °C in the absence of oxygen. Pyrolysis of the polymer gave a ceramic with a yield of about 70%.

PREPARATION AND PROPERTIES OF BULK CERAMICS VIA PYROLYSIS OF POLYCARBOSILANE WITH ACTIVE FILLERS I. EVOLUTION PROCESS IN ACTIVE FILLER CONTROLLED PYROLYSIS

The pyrolytic process of polycarbosilane (PCS) with active fillers (Ti, TiH 2, TiB 2, Cr, CrSi 2) is investigated. The ceramic yields with active fillers reach over 100% in N 2 atmosphere, and no shrinkage occurs when 12vol% Ti, or 4vol% Cr, or 3vol% CrSi 2 is added into PCS. XRD patterns indicate that metal carbides and nitrides form by reacting with gaseous evolution and N 2.

Study on the Pyrolysis Behavior of Polycarbosilane

The pyrolysis behavior of polycarbosilane （PCS） and chemical reaction mechanism during the pyrolysis process were studied by thermogravimetric-mass spectrometry （TG-MS） combined with X-ray diffraction and infrared spectroscopic analysis methods. The experimental results indicate that the main gas phase products generated during pyrolysis of PCS in nitrogen atmosphere include H2, -CH3 and CH4. The heating rate has a large effect on the pyrolysis process of PCS, the lower heating rate releases more small molecule gases and gets bigger rate of pyrolysis mass loss, demonstrating that the lower heating rate is beneficial to fully pyrolysis of PCS and obtain ceramics products with better microstructure.

Synthesis and ceramization of polycarbosilane containing beryllium

Polycarbosilane containing beryllium(BPCS) precursors was prepared by the reaction of polycarbosilane(PCS) with beryllium acetylacetone(Be(acac)2).The analysis of structures and components of BPCS demonstrates that their main structures are basically the same as PCS.Ceramization of BPCS precursors shows that BPCS precursors are organic below 600 °C and inorganic at 800 °C.At 1400 °C,BPCS precursors convert into silicon carbide ceramics.The ceramization of different beryllium content precursors were studied,which show that beryllium plays an important role in the inhibition of crystalline grain growth of β-SiC at high temperature and it can adjust the dielectric constant of silicon carbide ceramics.

A MORPHOLOGICAL STUDY OF POLY(DIVINYLBENZENE-co-ACRYLIC ACID) IN CROSSLINKING PRECIPITATION POLYMERIZATION

Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobutyronitrile） （AIBN） as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units.

PREPARATION AND PROPERTIES OF BULK CERAMICS VIA PYROLYSIS OF POLYCARBOSILANE WITH ACTIVE FILLERS II.FLEXURAL STRENGTH AND ANTI-OXIDATIVE PROPERTIES OF ACTIVE FILLER/PCS DERIVED BULK CERAMICS

The flexural strengths and oxidative resistant properties of the ceramics derived from polycarbosilane and active fillers (Ti, TiH 2, TiB 2, Cr, and CrSi 2) were measured and characterized. The introduction of active fillers enhances slightly the flexural strengths, and further densification is required to obtain higher strengths. The oxidative resistant behaviors of the specimens with active fillers are, by means of weight gain in air, poorer compared with those without active fillers.

Thermal stability and curing kinetics of polycarbosilane fibers

Thermal stability and curing kinetics of polycarbosilane (PCS) fibers were studied by thermogravimetry (TG), Fourier transform infrared spectroscopy(FT-IR). Curing is an essential step in the preparation of SiC fibers and the properties of SiC fibers are affected greatly by curing conditions. TG measurement performed in air shows that mass gain starts at approximately 200℃ and PCS fibers are sensitive to oxygen. Curing with oxygen, which results in crosslinking on the surface, enabled PCS fibers to retain its shape during high-temperature pyrolysis. The curing of PCS fibers is oxidation of Si─H and Si─CH3, then Si─O─Si and Si─O─C bonds are formed. This is a first order reaction, with activation energy of 79.27 kJ/mol, and the pre-exponential factor is calculated as 3.07×106. The kinetics model was obtained and the experimental data of PCS fibers show good agreement with the kinetics model.

Method for Control of Particle Size and Morphology of Paraffin/Polystyrene-Divinylbenzene Microcapsules

Microencapsulation of phase change materials(Micro PCMs) has been paid special attention because of their extensive applications in saving and releasing energy. Micro PCMs containing paraffin with a melting point of 55 ℃ in polystyrene-divinylbenzene(P(St-DVB)) were prepared by suspension-like polymerization. The characterization of microcapsules by FTIR, DSC and TG proved that paraffin had been successfully encapsulated and the proportion of encapsulated paraffin was 49.8%—58.5%. The effects of polyvinylpyrrolidone(PVP) with different molecular weights serving as the suspension stabilizer were investigated in detail. The results illustrated that the type of PVP had a significant influence on the particle size of Micro PCMs. The average diameter of Micro PCMs decreased with an increasing molecular weight of PVP. Moreover, the crosslinker-postaddition method was adopted in this study to improve the morphology of P(St-DVB) Micro PCMs. SEM images showed that when the DVB was added at the 2nd hour of polymerization the morphology of obtained P(St-DVB) Micro PCMs exhibited good sphericity since it could avoid the influence of cross-linker agent during the nucleation period.

Synthesis of Poly(styrene-co-divinylbenzene)-supported Dichloro Cyanuric Acid

ＳｙｎｔｈｅｓｉｓｏｆＰｏｌｙ（ｓｔｙｒｅｎｅ┐ｃｏ┐ｄｉｖｉｎｙｌｂｅｎｚｅｎｅ）┐ｓｕｐｐｏｒｔｅｄＤｉｃｈｌｏｒｏＣｙａｎｕｒｉｃＡｃｉｄＺＨＯＮＧＪｉｎｇ－ｆａｎｇ＊，ＬＩＣｈｅｎ－ｘｉ，ＨＥＢｉｎｇ－ｌｉｎａｎｄＷＵＺｈｉ－ｚｈｏｎｇ（Ｓｔ...

Synthesis of Monodisperse Poly(chloromethylstyrene divinylbenzene)Particle and Its Applications

Monodisperse poly (chloromethylstyrene divinylbenzene) particles were prepared by a two-step swelling method. It was demonstrated that the packings have comparative advantages for biopolymer separation with high column efficiency, low interstitial volume and low back pressure to the packings prepared with suspension polymerization method. Using size exclusionchromatography and weak ion exchange chromatography as examples, it was shown that these packings could be modified chemically more easily than poly (styrene divinylbenzene) packings.

Preparation and Characterization of Poly(divinylbenzene) Microcapsules Containing Octadecane

Poly(divinylbenzene) (PDVB) microcapsules containing octadecane (OD) (PDVB/OD) used as heat storage material were synthesized by suspension polymerization at 70 Microencapsulation, Microcapsule, Heat Storage Material, Octadecane, Suspension Polymerization, Poly(Divinylbenzene)C using benzoyl peroxide and polyvinyl alcohol as initiator and stabilizer, respectively. Thermal properties and stability of PDVB/OD microcapsules were determined using differential scanning calorimeter (DSC) and thermogravimetric analyzer. The morphology and structure of microcapsules were characterized by optical microscope, scanning electron microscope and fourier transform infrared spectrophotometer. From DSC analysis, the melting temperature of encapsulated OD (28oC) was almost the same as that of bulk OD (30oC) while it was quite different in the case of the solidification temperature (19oC and 25oC for encapsulated and bulk OD, respectively). The latent heats of melting (184.0 J/g-OD) and solidification (183.2 J/g-OD) of encapsulated OD were reduced from those of bulk OD (241.7 and 247.0 J/g, respectively). However, the prepared PDVB/OD microcapsules are able to be used for heat storage applications.

GRAFTED STYRENE-DIVINYLBENZENE COPOLYMERS CONTAINING BENZALDEHYDES AND THEIR WITTIG REACTIONS WITH VARIOUS PHOSPHONIUM SALTS

A chloromethylated styrene-divinylbenzene copolymer support system functionalized with 4-benzaldehyde and 2-benzaldehyde was prepared. The degree of functionalization with aldehyde groups is well suited for the subsequent use of the products as Wittig reagents. The polymer bound aldehyde was reacted with Wittig reagents to give olefin groups grafted on styrene-divinylbenzene copolymers. The reactions were carded out in phase transfer catalysis conditions. A simple procedure for the calculation of the degree of functionalization and the statistical modeling of the structural repetitive unit of the copolymer are reported.

PREPARATION OF PARTICLE SIZE NARROWLY DISTRIBUTED LOW-DENSITY STYRENE DIVINYLBENZENE COPOLYMER MICROBEADS

In view of the importance of dispersion agent,the amount of the crosslinking monomer and the diluent in suspension polymerization for the production of particle size narrowly distributed low-density stryene divinylbenzene copolymer microbeads(LDPS),their actions are preliminarily investigated in this paper.Experimental results indicate that when both the gelatine and polyvinyl alcohol(PVA)are used dispersion agents,the better effect is achieved,DVB is helpful to the formation of the lower density fine particles,the proportionof the DVB/St should be between 1:1-1.5:1.Compared with toluene,gasoline is the more effective diluent for the above target.

A Comparative Evaluation of Polystyrene Divinylbenzene Copolymer HPLC Columns on the Chromatographic Performance of the Compendial Method for Doxycycline Hyclate Capsules: Implications for Method Implementation of a Medical Countermeasure Medication

The purpose of this study was to evaluate the impact of polystyrene divinylbenzene copolymer HPLC columns on the chromatographic performance of the USP compendial method for doxycycline hyclate. The compendial method was implemented based on the assessment of the chromatographic performance of six USP defined L21 polystyrene divinylbenzene HPLC columns. Modifications to the method were based on USP for chromatography. The method was validated for the determination of doxycycline hyclate and its impurities in commercially available drug products. A number of different polystyrene-divinylbenzene columns were tested and failed to provide selectivity for the resolution of doxycycline and its impurities. Separation was optimally achieved on an Agilent PLPR-S column (250 × 4.6 mm, 8 μm) by using an Agilent 1260 series HPLC system. Doxycycline hyclate and its impurities were eluted isocratically at a flow rate of 1 mL/min with mobile phase and detected at 270 nm. The column temperature was maintained at 60oC. The method was validated according to USP category I requirements for Assay. Validation acceptance criteria were met in all cases. The analytical range for doxycycline hyclate was 50 - 250 μg/mL and the linearity was r2 > 0.999 over three days. The method was determined to be specific. Both accuracy (95.1% - 102.4%) and precision (0.50% - 4.8%) were established across the analytical range for low, intermediate and high QC concentrations. Method applicability was demonstrated by analyzing marketed products of doxycycline hyclate, in which results showed potency meeting USP acceptance criteria. In conclusion, this study described the remarkable differences in selectivity that were encountered during the implementation phase for the compendial methods for doxycycline and its impurities in marketed products and it could be used in the future to assss the product quality of doxycycline hyclate capsules stored in the National stockpiles.

Highly efficient Rod-shape Poly(methacrylic acid-co-styrene-codivinylbenzene)High-performance Liquid Chromatographic Column

A highly efficient copolymer (methacrylic acid - co - styrene - divinylbenzene) in situ making high-performance liquid chromatographic column was prepared and evaluated. The column efficiency calculated in terms of height equivalent to a theoretical plate was 25 mu m and rapid separations of small molecules such as substituted aromatic hydrocarbons and aromatic acids were achieved within five minutes.

High Oil-absorptive Composites Prepared from Non-woven Fiber and Sponges with 4-tert- butylstyrene-EPDM-divinylbenzene Graft Polymer

4-tert-butylstyrene-EPDM-divinylbenzene graft terpolymer (PBED) was prepared by graft cross-polymerization in toluene using BPO as an initiator. The gel-PBED and solPBED were isolated from extraction of tetrahydrofuran (THF), and then they were identified by IR spectroscopy. The maximum oil-absorptivity of gel-PBED produced from the optinum reaction conditions was 8 420% but its swelling rate was very low. The highest oil-absorptivity of photocrosslinked sol-PBED film was 5 800%. Although its oil absorbency was not as high as gel-PBED' s, swelling rate was higher than that of gelPBED and was suitable for commercial purpose. After swelling in oil, neither gel PBED nor photocrosslinked sol-PBED film having high oil-absorptivity had sufficient mechanical strength to be taken out of oil wholly. As is known, composite technique is one of the useful methods for reinforcing them. Fibers, sponges and non-woven cloths were used as reinforcers or supporters in this work. Oil-absorptivities and swelling kinetics were evaluated by method ASTM (F726 - 81 ) and an experimental equation. The mechanical properties and the morphologies of some composites were measured by tensile tester and SEM , respectively.

聚碳硅烷改性碳化硅陶瓷膜的制备及其性能研究

通过包覆法制备了聚碳硅烷包覆的碳化硅粉末,对其制备的生坯进行烧结,得到膜形态良好的碳化硅陶瓷膜。利用扫描电子显微镜、激光共聚焦显微镜、压汞仪和截留测试等手段分析了膜的形貌和截留性能。结果表明,聚碳硅烷在膜层的烧结过程中具有粘结作用,包覆量为5%时,膜层表面平整无裂缝,膜层形态较好。碳化硅初始骨料粒径为0.3μm,聚碳硅烷包覆量为5%,烧结温度为1750℃时,制备的膜层孔径为0.842μm,对100 nm微球截留率高达89%。研究表明,聚碳硅烷在碳化硅膜层形态及孔径控制方面应用优势明显。

多壁碳纳米管杂化改性苯乙烯-二乙烯基苯共聚物载体的制备及性能

苯乙烯-二乙烯基苯共聚物(SDB)为载体的Pt/SDB疏水催化剂是氢-水液相催化交换(LPCE)技术的重要材料。针对SDB载体疏水性不强和强度低等问题,通过KH570,KH560和KH550硅烷偶联剂改性多壁碳纳米管(MWCNTs),再杂化改性SDB载体。结果表明:杂化改性的SDB载体的水接触角提高了20°以上,抗压强度为基础SDB载体的1.6~3.8倍,热重分析的初始热分解温度提高了4.6~15.8℃。KH570处理的MWCNTs含有双键,可实现与苯乙烯、二乙烯基苯的三元共聚且掺杂均匀,杂化改性SDB载体效果最佳。

基于离子交换的Ag^(+)修饰聚合物填料的制备及其性能研究

金属离子与不同结构的分析样品之间可产生特异性相互作用,因此金属离子修饰的色谱填料具有特殊的分离选择性。该文以粒径均一、比表面积大、孔径均匀的聚苯乙烯-二乙烯基苯微球为基质,采用浓硫酸对微球中的苯基进行磺化处理,使其被修饰上磺酸基团,具备阳离子交换的功能。并进一步采用离子交换法,将填料上的H+交换成Ag^(+),制备了具有分离选择性的Ag^(+)修饰聚合物填料。随后将该填料装填成固相萃取(SPE)小柱探讨了其稳定性、使用条件及分离选择性。该文所发展的Ag^(+)修饰聚合物填料具有制备方法简单、稳定性好、对离子吸附能力强等特点,具有良好的分离选择性,装填成SPE柱可满足复杂实际样品预处理的需要。

三种温和还原法制备Pt/SDB

Pt/SDB是液相催化交换(LPCE)反应处理核电产生含氚废水的一种很有前途的催化剂。采用悬浮聚合法制备得到介孔聚苯乙烯-二乙烯基苯(SDB),以硼氢化钠(SBH)、水合肼(HH)或乙二醇(EG)为还原剂,温和还原法制备SDB载体负载铂活性颗粒,产物分别记为Pt/SDB-SBH、Pt/SDB-HH或Pt/SDB-EG。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、氮气吸附脱附和氢-水催化交换实验等对其结构形貌及催化活性表征。结果表明:Pt/SDB-SBH疏水催化剂具有突出的性能和优异的催化活性,Pt纳米颗粒平均粒径约为3.3 nm,Pt^(0)组分比例为72.0%,催化交换柱效率达65.0%,并在120 min保持稳定。为低温还原制备Pt/SDB疏水催化剂提供了一种新的策略。