Nanocomposites of a Silicon-containing Arylacetylene Resin with Octakis(dimethylsiloxy)octasilsesquoixane

Nanocomposites（PMSEPE/Q8M8^H） were prepared via solution blending of octakis（dimethylsiloxy）octasilsesquoixane（Q8M8^H） into poly（dimethylsilyleneethynylenephenyleneethynyle ne）（PMSEPE）. PMSEPE/Q8M8^H nanocomposites were characterized by Fourier transform infrared（FT-IR） spectroscopy, rheological measurement, differential scanning calorimetry（DSC）, scanning electron microscopy（SEM） and thermal gravimetric analysis（TGA）. The experimental results show that the hydrosilylation reaction in PMSEPE/Q8M8^H nanocomposites occurs slowly exceeding 180 ℃. PMSEPE/Q8M8^H nanocomposites can be cured at temperatures less than 260 ℃ and the cube structure of Q8M8^H keeps stable during the curing process. POSS domains are evenly dispersed in the cured nanocomposite. However, serious aggregation of POSS occurs at 15% Q8M8^H content. The thermal and thermooxidative stabilities of PMSEPE/Q8M8^H nanocomposites obviously depend on the content of Q8M8^H. The incorporation of Q8M8^H can effectively enhance the thermal and thermooxidative stabilities of cured PMSEPE. PMSEPE/Q8M8^H nanocomposites can be the candidates for applications in high temperature environment.

Studies on Silicon-Containing Fragrance Raw Materials( Ⅱ )——Syntheses and Odors of 4-Trimethylsilylcyclohex-3-enol and 4-Trimethylsilylcyclohexanol Derivatives

1-Substituted- 4-trimethylsilylcyclohex- 3-enol and 1-substituted- 4-trimetnylsilyl-cyclohexanol, 4-trimethylsilylcyclohex-3-enol and 4-trimethylsilylcyclohexanol, and some of their esters and carbon counterparts were synthesized. Structures of the nineteen new compounds were determined by 1H NMR, IR and MS. Their odors are evaluated.

Synthesis of Branched Silicon-Containing Arylethyleneacetylene Resin and the Performance of Casting

With good thermal properties, dielectric property and high-temperature ceramics performance, silicon-containing arylacetylene resin (PSA) has opened an attractive alternative to high performance thermosetting resins in application in the area of aircraft and missile. However, it is difficult to introduce silicon into the main chain of organic arylacetylene. In this paper, branched silicon-containing arylethyleneacetylene (BSA) resin was synthesized by methyltrichlorosilane and diethynylbenzene with zinc powder as catalyst. The advantages lie in simple operation, short reaction period and mild heat release. BSA resin exhibits excellent processability with the processing temperature of 20?C - 150?C and processing window of 130?C. The glass transition temperature of the resin casting is over 500?C. The temperature of 5% weight loss (Td5) is up to 575?C and char yield of thermoset at 800?C (Y800) reaches 91% under nitrogen. Also, the dielectric constant and dielectric loss of casting has no change within 10 - 106 Hz.

Evaluation of Application Effect of Silicon-containing Water-soluble Fertilizer on Fast Vegetables

[Objectives]The study aims to verify the application effect of silicon-containing water-soluble fertilizer on fast vegetables.[Methods]Two vegetable crops,rape and lettuce,were studied,and three treatments were set up,including treatment 1(conventional fertilization+foliar spraying of silicon-containing water-soluble fertilizer,treatment 2(conventional fertilization+foliar spraying of the same amount of clear water),and treatment 3(conventional fertilization).[Results]The yield of lettuce and rape in treatment 1 increased by 15.1%and 8.6%,respectively;compared with treatment 3,the yield of lettuce and rape rose by 18.6%and 10.9%,respectively.Variance analysis shows that the F values of lettuce and rape were 20.938 and 35.372,respectively,and the differences among various treatments were extremely significant.[Conclusions]The application of silicon-containing water-soluble fertilizer on lettuce and rape significantly increased their yield.

Preparation and Characterization of Cyano-Silicon-Containing Arylacetylene Resins and Their Composites:Dual Enhancement Strategy Involving Physical Interfacial Interactions and Chemical Crosslinking

Silicon-containing arylacetylene (PSA) resins have broad application prospects because of their excellent heat resistance.However,improving their mechanical properties and interfacial bonding with reinforcement fibers while maintaining heat resistance is a challenge in engineering applications.Here,poly(diethynylbenzene-methylsilyl-3-benzonitrile)(DEB-CN) and poly(diethynylbenzene-methylsilyl-3,6-diethynylcarbazole-3-benzonitrile)(DEC-CN) were synthesized via an isopropylmagnesium chloride lithium-chloride complex (i-PrMgCl·LiCl),overcoming the compatibility problem between cyano groups and Grignard reagents.The cyano and alkyne groups in the resin underwent cyclization to form pyridine,catalyzed by the-NH-moiety in DEC-CN,resulting in extremely high thermal stability (5%weight loss temperature:669.3°C,glass transition temperature>650°C).The combination of cyano dipole-dipole pairing and hydrogen bonding greatly enhanced the resin-fiber interface properties,while the generated pyridine promoted stress relief in the crosslinked network,substantially improving the mechanical properties of the cyano-silicon-containing arylacetylene resin composites.The flexural strength of quartz fiber cloth/DEC-CN composites was 298.2 MPa at room temperature and 145.9 MPa at 500°C,corresponding to 84.0%and 127.6%enhancements,respectively,over the cyano-free counterpart.These cyano-silicon-containing arylacetylene resins exhibited a dual reinforcement mechanism involving physical interfacial interactions and chemical crosslinking,achieving a good balance between thermal stability and mechanical properties.

含硅芳炔树脂的固化及其复合材料性能

通过溶液法在含硅芳炔树脂(PSA)中加入催化剂乙酰丙酮镍和三苯基膦,制备了碳纤维增强PSA复合材料(T700CF/PSA),研究PSA树脂的热自聚固化和催化固化反应动力学、固化树脂的热性能和复合材料的弯曲性能。结果表明:PSA中加入催化剂可降低其固化温度,初始表观活化能下降,但后期固化表观活化能提高。加入催化剂后的PSA的热稳定性略高于未加催化剂的PSA,800℃氮气氛围中残留率达88%。单向碳纤维T700CF增强PSA基复合材料室温下的弯曲强度为1 805 MPa,弯曲模量为149 GPa,300℃下弯曲强度和弯曲模量的保留率分别为73%和93%,其玻璃化转变温度高于500℃。T700CF增强含催化剂的PSA基复合材料的弯曲模量提高,但室温下弯曲强度略有降低。

CHARACTERIZATION OF A MODIFIED SILICON-CONTAINING ARYLACETYLENE RESIN WITH POSS FUNCTIONALITY

A modified silicon-containing arylacetylene resin with a well-defined organic-inorganic POSS functionality was successfully synthesized by Huisgen azide-alkyne 1,3-dipolar cycloaddition. The POSS hybridized resin exhibits excellent thermal properties which were characterized by differential scanning calorimetry （DSC） and thermogravimetric analyses （TGA）. Scanning electron microscope （SEM） was used to characterize fracture surface of the hybridized polymer. The results show that phase separation occurs. The POSS moieties are aggregated each other in the polymer to form 200-400 nm domains.

Investigation on poly[(methylsilylene ethynylene phenylene ethynylene)-co-(tetramethyldisiloxane ethynylene phenylene ethynylene)]

Poly[(methylsilylene ethynylene phenylene ethynylene)-co-(tetramethyldisiloxane ethynylene phenylene ethynylene)]was synthesized by polycondensation reaction of m-diethynylbenzene magnesium reagent with 1,3-dichlorotetramethyldisiloxane and dichloromethylsilane.The copolymer was characterized by FT-IR,~1H NMR,differential scanning calorimetry and thermogravimetric analysis.The results show that the copolymer exhibits good processability and cures at low temperatures.The cured copolymer shows high thermal stability.

SYNTHESIS AND CHARACTERIZATION OF POLY[(METHYLSILYLENE ETHYNYLENEPHENYLENEETHYNYLENE)-CO-(DIMETHYLSILYLENE ETHYNYLENEPHENYLENEETHYNYLENE)]S

A series of poly[（methylsilylene ethynylenephenyleneethynylene）-co-（dimethylsilylene ethynylenephenyleneethynylene）]s were synthesized by the incorporation of various ratios of methylsilylene to dimethylsilylene units into the polymer chain backbone. The resultant copolymers were soluble in a variety of common organic solvents at room temperature. The copolymers were characterized by FT-IR, ^1H-NMR, GPC, rheological analysis, differential scanning calorimetry （DSC） and thermogravimetric analysis （TGA）. The results showed that the copolymers exhibited good processability and cured at low temperatures like 200℃. The curing reactions involved in hydrosilylation of Si-H and alkyne groups and the polymerization of alkynes. Td5 （5% weight loss） of the cured copolymers ranged from 629℃ to 686℃, and the decomposition residues of cured copolymers at 1000℃ ranged from 88.1% to 90.9% under nitrogen. Thermal stability of the copolymers increased with the introduction of methylsilylene traits into polymer chains. The cured copolymers were sintered at 1450℃, and the results of X-ray diffraction analysis showed that β-SIC was formed in the sintered products.

Synthesis and Characterization of Compounds Containing 1,2,3-Triazole via Click Reaction and Ag(Ⅰ) Complex

In this work, 1,4-bis(4-phenyl-1,2,3-triazole)benzene, 1,3-bis(4-phenyl-1,2,3-triazole)propane, bis(1-phenyl-1,2,3-triazole)-methylphenylsilane, and 1-ally-4-phenyl-1,2,3-triazole have been designed and synthesized via Click reaction. Fourier transform infrared spectroscopy(FT-IR) and nuclear magnetic resonance spectroscopy(NMR) were used to confirm the compounds' structures. The effect of silicon atom on the optical properties has also been studied. The UV-vis absorption wavelength of silicon-containing compound is about ca. 10 nm red-shifted when compared with that of other three compounds. The fluorescence emission bands of the compounds in CHCl_3 solutions were observed around ca. 440 nm. And the luminescent coordination compound, namely [AgL1?NO_3?3H_2O]n, based on the ligand 1-allyl-4-phenyl-1,2,3-triazole has been prepared. In addition, this complex exhibits a 1 D chain structure. The crystal structure has been determined by single-crystal X-ray diffraction, and the optical properties have been investigated by fluorescence spectrum. In summary, our work may provide new materials with luminescent property which is potentially useful in material fields.

Bainite Growth Behavior at Early Stage of Transformation in a High Carbon Silicon-Containing Steel

The growth behavior at the early stage of bainitic transformation was investigated using optical microscopy,X-ray diffraction analysis and transmission electronic microscopy.The bainite was obtained by isothermal transformation at 200 ℃ only for a short time in a high carbon silicon-containing steel after austenitization at 200 ℃ only for 20 min.Transmission electronic microscopy shows that the bainite appears in the form of plates with a width of about 30 nm,and that the interface of the bainite leading tip is wedge shaped.X-ray diffraction analysis reveals that the bainite plates consist of single ferrite phase,with absence of carbides.The results confirm the occurrence of the moiré which suggests the existence of austenite grain boundaries at the bainite leading tip.Both the lateral growth and longitudinal growth of bainite have weak ability to traverse the lattice-distortion strain fields and austenite grain boundary.The austenite grain boundary impedes the longitudinal growth of the bainite plate,i.e.,the growth of bainite plate stops at the austenite grain boundary.The longitudinal growth of bainite associated with the features of shear mechanism can not completely be in accordance with that of martensitic transformation.

Studies on silicon-containing fragrance raw materials——I. Syntheses and structure-odor relationship of acetals of 4-trimethylsilyl-3-cyclohexenone and 4-trimethylsilylcyclohexanone and their carbon counterparts

In order to investigate the structure-odor relationship of odoriferous compounds and search for new aroma chemicals, seven acetals of 4-trimethylsilyl-3-cyclohexenone and their carbon counterparts were synthesized by Birch reduction of 4-substituted anisoles and then acetalization. Seven acetals of 4-trimethylsilylcyclohexanone and their carbon counterparts were synthesized similarly. Structures of all new compounds were determined by MS, IR and ~1H NMR, and their characteristic odors were evaluated as well. The characteristic odors of the acetals formed by 4-substituted-3-cyclohexenone and 1, 2-diols are fruity and woody. The acetals formed from 1, 3-diols are woody, and formed with 1, 4-diols are very faint in odor. Odors of acetals of 4-substituted cyclohexanone are all very weak. As a whole, odors of organosilicon compounds are weaker, but somewhat more delicate than their carbon counter- parts.

Copolymerization and Properties of Multicomponent Crosslinked Hydrogels

A series of multicomponent hydrogels were prepared by the copolymerization of hydrophobic silicon-containing monomer 3-bis（trimethylsilyloxy） methylsilylpropyl glycerol methacrylate（Si MA） with the solvent-responsive monomers 2-hydroxyethyl methacrylate（HEMA） and N-vinyl pyrrolidone（NVP） and thermosensitive monomer N,N-dimethyl acrylamide（DMA）. 2-Hydroxy-2-methyl phenyl acetone（D-1173） was chosen as UV initiator and five different dienes/triene monomers were selected as crosslinking agent in order to select the best crosslinker. The ethanol extraction experiments as well as the FTIR, DSC and TG results showed that the copolymerization was effective. The optical, permeability, and mechanical analysis results demonstrated that the obtained hydrogels were highly transparent with good oxygen permeability and mechanical properties. And the impact of crosslinker on the mechanical properties of the hydrogels was also discussed in detail. The basic results demonstrated that the obtained hydrogels had good stimuli-responsive effects to both p H value and solvent.