Catalyzed Nonhydrolytic Sol-Gel Route to Organosilsesquioxane Gels

Methyl-, vinyl- and octadecylsilsesquioxane gels have been prepared by the solvent-free nonhydrolytic condensation of organotrichlorosilane with oxygen donors in the presence of a catalytic amount of various metal chlorides. Pure phenylsilsesquioxane gels could not be obtained by this route owing to the partial ipso-cleavage of phenylsilicon bonds by the alkyl chloride formed during the condensation process. The rate of condensation depends on the nature of both the oxygen donor and the catalyst. For highly condensed methylsilsesquioxane gels, the extent of silicon loss by Si–O/Si–O and Si–C/Si–O redistribution reactions during pyrolysis depends mainly on the nature of the oxygen donor, whilst the composition of the volatile silicon species, and consequently that of the residue, depends on the nature of the metal chloride initially introduced. This process allows the formation of a rather well-condensed octadecylsilsesquioxane gel which is constituted of small particles assembled by crystallization of the long C18 chain.     

Deactivation by polysiloxane and phenyl containing disilazane: A 29SI CP-MAS NMR study after the formation of polysiloxane chains at the surface

A high degree of deactivation of glass and fused-silica capillary column walls is attainable by means of high temperature silylation (HTS) with or without a preceding leaching process. HTS with a phenyl containing disilazane, diphenyltetramethyldisilazane (DPTMDS), and polydimethylsiloxane (PDMS) are studied on Cab-O-Sil, a fumed silica, as a model substrate. Using ²⁹Si CP-MAS NMR, it was shown that no dimethylsiloxane chains were formed upon silylation with DPTMDS under different conditions of humidity and stoichiometry at 377°C. With DPTMDS deactivation it is possible that amino trisiloxy silane groups are formed, these groups add extra activity to the surface. Silylation with a PDMS, OV 101, at various temperatures between 300°–420°C did show that dimethylsiloxane chains were bonded at the surface. Using the ²⁹Si CP-MAS NMR technique with variable contact times to reveal siloxy group mobility, the degradation of dimethylsiloxane chains at the surface was studied. PDMS degradation at an optimal temperature gives a more effective diminuation of the silane activity caused by chemical reaction with the silanol groups and the effective screening of the remaining silanol groups with anchored polydimethylsiloxane chains and small cyclodimethylsiloxane ring structures at the surface.     

Facile synthesis of meso-substituted dipyrromethanes and porphyrins using cation exchange resins

The macroporosity and acidity of cation exchange resins play a crucial role in the synthesis of dipyrromethanes and porphyrins; for the first time, cation exchange resins have been used as heterogeneous solid acid catalysts to produce dipyrromethanes and porphyrins in good yields. The reaction, at room temperature, of substituted aromatic aldehydes with pyrrole catalysed by cation exchange resin afforded the corresponding meso-substituted dipyrromethane in yields ranging from 70 to 80%, indicating the broad scope of the reaction. Further, the condensation of meso-substituted dipyrromethane with similar or different substituted aromatic aldehydes, using cation exchange resins furnished meso-tetrakis-symmetrical and mixed porphyrins, respectively. One-pot synthesis of porphyrins can also be carried out directly from the aldehydes and pyrrole under the above conditions. Acidolysis of the dipyrromethane is negligible under the conditions of the porphyrin-forming reaction.     

Modification of epoxy-novolac resins with polysiloxane containing nitrile functional groups: synthesis and characterization

Synthesis of the statistical epoxidized polycyanopropylmethylsiloxane-co-polydimethylsiloxanes (PCPMS-co-PDMS) has been demonstrated. The modified polysiloxanes were prepared via a two-step method; (1) the ring-opening polymerization of octamethylcyclotetrasiloxane (D₄) and tetramethylcyclotetrasiloxane (D₄H), (2) hydrosilylation reaction of the polysiloxane prepolymers with allyl cyanide and allyl glycidyl ether. Molar ratios of D₄H and D₄ were varied to produce the modified polysiloxanes with differences in polarity. ¹H-NMR, ²⁹Si-NMR, ¹³C-NMR and FTIR were used to monitor the formation of the modified polysiloxanes and DSC was used to study their thermal behaviors (T_g, −118 to −68 °C). The use of the modified polysiloxanes as an elastomeric component in epoxy-novolac networks was also investigated. TEM and their transition temperatures suggested that the epoxy-novolac networks with high content of PDMS modifiers exhibited microphase separation. The fracture toughness properties of the networks with the polysiloxane modifiers were improved over the controls without polysiloxanes.     

Synthesis of hybrid resins via polysiloxane with methacryloyloxy groups

A polysiloxane derivative with methacryloyloxy groups (MPS) that was obtained from the reaction of polymeric tributylstannyl ester of silicic acid and (3‐methacryloyloxypropyl)dimethylchlorosilane was demonstrated to be a useful inorganic component for the preparation of organic–inorganic hybrid resins as nanocomposites. The copolymerizations of MPS with common monomers such as styrene, acrylonitrile, and methyl methacrylate proceeded readily at room temperature under UV irradiation to give the corresponding resins in good yields. The resins obtained from MPS and methyl methacrylate showed good transparency, hardness in a scratch test, and resistance to toluene but had poor flexibility. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1–7, 2001     

One‐step synthesis of polysiloxane graft polyethylene mimic: Non‐expensive compatibilizer for polyethylene/polysiloxane blend

Polysiloxane/polyolefin copolymers have drawn much attention recently and emerged as a new group of functional polyolefin since they possess distinctive properties and find great potential applications in many areas (eg, compatibilizer, processing aid and surface modifier). However, traditional routes to synthesize polysiloxane/polyolefin copolymers generally require multi‐step labor‐consuming procedures. Herein, we report a novel one‐step synthesis of polydimethylsiloxane graft polyethylene (PDMS‐g‐PE) mimics. It was found that PDMS‐g‐PE mimics, namely vinylmethylsiloxane‐dimethylsiloxane‐(C30‐45 alkyl)methylsiloxane copolymers (short for VD‐AMS), could be formed via a one‐step synthetic procedure based on the siloxane equilibrium process between silanol‐terminated vinylmethylsiloxane‐methylsiloxane copolymer and (C30‐45 alkyl)methylsilicone. The chemical structures of VD‐AMS were characterized unambiguously using Fourier transform infrared spectroscopy, nuclear magnetic resonance, gel permeation chromatography, differential scanning calorimetry. The correlation between reaction conditions and the structural parameters of VD‐AMS was established. Based on our experimental results, a plausible mechanism for the synthesis of VD‐AMS was proposed. Scanning electron microscopy micrographs showed that VD‐AMS could function as an efficient compatibilizer for immiscible PE/silicone blend. Given that the precursors of VD‐AMS are commercially available with low prices and that VD‐AMS can be easily synthesized under mild conditions, we believe VD‐AMS can represent as a competitive potential compatibilizer due to its relatively low cost.     

Flame retardancy and flame retarding mechanism of high performance hyperbranched polysiloxane modified bismaleimide/cyanate ester resin

A novel kind of modified bismaleimide/cyanate ester (BCE) resins by copolymerizing with hyperbranched polysiloxane including high content of phenyl (HBPSi) was first reported. The effect of HBPSi on the curing mechanism, and that on the dielectric properties and flame retardancy of cured networks were systemically investigated. Results show that compared with BCE resin, HBPSi/BCE resin has obviously different cross-linked structure, and thus leading to simultaneously improved dielectric properties and flame retardancy. The reactions between HBPSi and the decomposition structure of BCE resin change the thermo-oxidative degradation mechanism of the first step in the thermo-oxidative degradation; in addition, the presence of HBPSi in BCE resin also significantly reduces the mass loss rate (MLR) and increases char yield at 800 °C under an air atmosphere. Therefore, the positive effect of HBPSi on improving the flame retardancy is attributed to the condensed phase mechanism. On the other hand, HBPSi/BCE resins exhibit improved dielectric properties (including decreased dielectric constant and loss) with increasing the content of HBPSi. More importantly, this investigation demonstrates that designing new polysiloxane with suitable chemical structure is important to develop high performance resins with attractive flame retardancy and dielectric properties.     

Preparation,characterization and application of polyaniline/epoxide polysiloxane composite films

Composites of polyaniline(PAn) and epoxide polysiloxane(EPSi) are reported for the first time. EPSi is designed, synthesized and N-grafted onto the PAn backbone through covalent bonds. As-prepared EPSi-g-PAn composites are soluble in organic solvents and the corresponding films can be easily produced via a simple solution-casting procedure. The composite films combine the mechanical characteristics of EPSi and the chemical properties of PAn, enabling the facile introduction of the noble metal particles. The successful fabrication of the composites is confirmed by the investigation of the molecular structure, crystalline structure and microstructure of the materials. The resulting composite films containing noble metal particles are employed as the catalysts for the hydrogenation of phenol to produce cyclohexanone, which exhibit the convenience and recyclability for usage as well as the high catalytic activities, including the conversion ratio of 97%-100% and the selectivity as high as 84%-98%. The present work not only provides a new method to improve the processability of the conducting polymers but also describes a kind of composite materials that may display outstanding preformances in industrial catalysis.     

The relationship between the compatibility and thermodegradation stability of modified polyetherimide/bismaleimide resins by hyperbranched polysiloxane with high degree of branching

Amino‐terminated hyperbranched polysiloxane (AHBSi) with high degree of branching (0.8) is used to improve the compatibilization of polyetherimide (PEI)/allyl bisphenol A modified bismaleimide (BD) blend. The relationship between the compatibility and thermal/thermal‐oxidative stability of the AHBSi/PEI/BD system is intensively investigated. Although PEI has high thermal stability, the PEI/BD blend has poorer thermal stability than BD resin due to the incompatibility. With the addition of AHBSi into the PEI/BD blend, AHBSi chemically connects PEI and BD, leading to the increased compatibility; moreover, interestingly, both thermal and thermo‐oxidative stabilities are significantly improved. Under a N₂ atmosphere, the addition of 0.5 wt% of AHBSi increases the initial degradation temperature of the PEI/BD blend from 395°C to 412°C. The thermodegradation kinetics were studied, and results show that the AHBSi/PEI/BD system has much higher activation energy of degradation in both N₂ and air atmospheres. The origin behind these interesting results is intensively investigated. Copyright © 2013 John Wiley & Sons, Ltd.     

Preparation and properties of polysiloxane grafting multi‐walled carbon nanotubes/polycarbonate nanocomposites

Carboxyl multi‐wall carbon nanotubes (MWNTs‐COOH) were grafted by diaminopropyl terminated dimethylpolysiloxane (DPD) to the modified MWNTs‐COOH (MWNTs‐DPD). The surface structure and thermal stability of MWNTs‐DPD and MWNTs‐COOH were characterized using Fourier‐transform infrared spectroscopy, X‐ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). Then PC/MWNTs‐COOH and PC/MWNTs‐DPD nanocomposites were prepared by the solution method and melt extrusion method. The mechanical properties, transmission electron microscopy (TEM), TGA, limiting oxygen index (LOI), UL‐94 test, and permittivity test were used to evaluate the properties of the composites. The results showed that the MWNTs‐DPD was dispersed well in the PC matrix, and its tensile strength, flexual strength, flexural modulus, and flame retardancy were better than that of PC/MWNTs‐COOH. MWNTs‐DPD can improve the electrical properties of the nanocomposites at the low loading in PC. Copyright © 2010 John Wiley & Sons, Ltd.     

聚醚-紫外侧基聚硅氧烷的结构表征与膜形态

利用聚甲基氢硅氧烷(PHMS)与4-(β-羟基-γ-烯丙氧)丙氧基-2-羟基二苯甲酮(MUV-O)、α-烯基聚醚(F6)的硅氢化加成反应,合成了一种新型聚醚-二苯甲酮衍生物侧基聚硅氧烷PE-PUVSi,用红外光谱(IR)、紫外光谱(UV)、核磁共振氢谱(1H-NMR)以及原子力显微镜(AFM)等仪器对产物的结构和成膜形态进行了研究。结果表明,新合成的PE-PUVSi对波长为243.6、289.2、325.0nm的紫外光有强吸收作用。在纤维及单晶硅表面,PE-PUVSi均可成膜。但宏观上平滑的PE-PUVSi膜,微观上实则呈非均一、相分离结构,其中UV侧基以纤细尖峰分布在聚硅氧烷膜表面,而亲水性聚醚基团则卷曲堆积成峰包。     

Preparation and structural determination of siloxane-modified sulfone-containing epoxy resins

Siloxane-modified sulfone-containing epoxy resins (ESBS) were prepared by polycondensation of PMPS and/or PDMS siloxane oligomers with EBS, the sulfone-containing epoxy resin. Structures were analyzed by IR, ¹H-, and ¹³C-NMR. The siloxane content in the copolymers was determined by ¹H-NMR with an integration technique. Epoxy equivalent weight (EEW) determination indicated that the oxirane ring of EBS was intact with this hot-melt procedure. The GPC measurement of these ESBS copolymers showed that molecular weight (MW) increased with increasing siloxane content in PMPS-modified copolymers. Evidence of siloxane incorporation in the copolymer was discussed. © 1996 John Wiley & Sons, Inc.     

Syntheses and NMR study of [(2-dimethylaminomethyl)phenyl]vinylsilane derivatives and [(2-dimethylaminomethyl)phenyl]ethylsilane derivatives

Various vinylsilanes, SiX(CHCH₂)(CH₃)[2-(CH₃)₂NCH₂C₆H₄], and ethylsilanes, SiX(CH₂CH₃)(CH₃)[2-(CH₃)₂NCH₂C₆H₄] [X=Cl (1); OMe (2); H (3); F (4); OSiMe₃ (5); NMe₂ (6); Me (7)], were synthesized in order to investigate the electronic effect of vinyl group on silicon atom having an intramolecular coordination arm. The magnitude of Δδ (ethyl→vinyl for ²⁹Si-NMR) of chlorosilane, 1, was the biggest one among 1-7. The differences of ²⁹Si chemical shifts between vinylsilanes and ethylsilanes increased in the following order: X=Me, NMe₂<H<OSiMe₃<OMe<F<Cl.     

Experimental design and modelling in the investigation of PECVD parameters effects on the structural and gas transport properties of plasma polysiloxane membranes

The experimental design method was used to investigate the PECVD parameters effects on the properties of plasma polysiloxane membranes synthesized using octamethylcyclotetrasiloxane or hexamethyldisiloxane as monomers. On a wide experimental range and with a minimum number of experiments, the use of such a statistical tool enabled us to set up complete and reliable correlations, in the form of polynomial models connecting the gas transport properties (H₂ permeability coefficient, H₂/N₂ ideal selectivity) and the structural properties (growth rate, density, organic/inorganic nature) of synthesized films with the two most influent synthesis parameters of the PECVD process: the input power (represented by the input voltage) and the monomer flux. The polynomial models enabled us not only to statistically confirm the effects of the PECVD parameters displayed by previous classical experimental studies, but also to model, in the mathematical sense, the evolution of each property of materials taking into account the first and second orders effects of both PECVD synthesis parameters. By the use of a performing statistical tool, we managed to improve the knowledge of relations between synthesis parameters/structure/properties relative to our process.     

Effect of amino and polysiloxane groups on the chemical adsorption of polymers containing thiophosphate at the oil/metal interface under extreme pressure

Copolymers that separately contained thiophosphate–polysiloxane, thiophosphate–amino, and thiophosphate–polysiloxane–amino groups were synthesized and characterized. The performances of these synthesized copolymers on metal surfaces under a high load and rotary velocity were examined by the measurement of the oil temperature, frictional coefficient, and electrical contact resistance between two metal surfaces. The configuration of the adsorption layer was studied with energy‐dispersive spectrometry (EDS) and scanning electron microscopy (SEM). Copolymers that contained amino–thiophosphate groups reduced the frictional coefficient between two metal surfaces and markedly limit the increase in the oil temperature. Notably, a higher content of polysiloxane groups in the copolymer corresponded to an increased operating time to establish the adsorption layer on the metal surface. However, a higher content of amino groups reduced the time required for the layer to form. The adsorption layers that formed on the metal surfaces were investigated by EDS as phosphides produced by a chemical reaction of the thiophosphate‐containing copolymer with the metal surface. These adsorption layers on the metal surface were directly observed with SEM. The layer that formed on the metal surface of copolymers containing less polysiloxane and more amino groups was the thickest layer for all the synthesized copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1795–1803, 2002     

Total synthesis and structural revision of engelhardione

The total synthesis of the macrocyclic natural product engelhardione is reported. This effort led to the structural revision of the published structure of engelhardione to that of pterocarine. The revision reflects the change of the substitution pattern of one phenyl ether ring from the meta to the para position. To confirm, pterocarine (2) and its close regioisomer 3 were subsequently synthesized for comparison. Moreover, to the best of our knowledge, our synthesis of 1 represents the first example of a 14-membered macrocyclic diarylheptanoid with a meta-meta substitution pattern at the diphenyl ether moiety.     

The synthesis and catalytic application of spacer-modified diol-functionalised Merrifield resins

A range of alkyl spacer-tethered 1,2- and 1,3-diols have been prepared from commercially available Merrifield resin (1) and (4-chloromethyl)phenylpentyl-polystyrene-co-divinylbenzene (2). The utility of these resin-bound diols as supports for the Ti(IV)-catalysed Diels-Alder reaction has been exemplified and it has been demonstrated that the length of the tether has a direct effect upon the catalytic activity.     

Microfluidic fabrication of polysiloxane/dimethyl methylphosphonate flame‐retardant microcapsule and its application in silicone foams

A novel and versatile route for fabricating flame‐retardant microcapsules via microfluidics technology is reported. The flame‐retardant microcapsules were prepared with a dimethyl methylphosphonate (DMMP) core and an ultraviolet‐curable (UV‐curable) polysiloxane shell. Furthermore, a UV‐curable polysiloxane was synthesized. The synthesis mechanism of UV‐curable polysiloxane and the curing mechanism of flame‐retardant microcapsules were analyzed. To verify that DMMP was encapsulated in the microcapsules, X‐ray fluorescence was used before and after microencapsulation. The resulting microcapsules were well monodispersed and exhibited a good spherical shape with a smooth surface. In addition, the size of the microcapsules decreased dramatically with an increasing flow‐rate ratio of the middle‐/inner‐phase or outer‐phase flow rate. The thermal stability of the microcapsules was worse than shell materials but superior to DMMP. Silicone foams (SiFs) with microcapsules prepared using a dehydrogenation method achieved a relatively higher limiting oxygen‐index value than the pure SiF, which indicated that the microcapsules could enhance the flame retardation of SiFs effectively. Because of the polysiloxane shell, the microcapsules had good compatibility with SiFs, and the influence of microcapsules on the mechanical properties of SiFs was unremarkable.     

Direct formylation of 2-pyridone core of 3-N-methylcytisine via Duff reaction; synthesis of 9-enyl, 9-ynyl and 9-imino derivatives

The first direct synthesis of 3-N-methyl-9-formylcytisine via electrophylic formylation is described. It is established, that Vilsmeier-Haack and Gatterman variants of this reaction are unsuccessful in the case with 3-substituted (-)-cytisine derivatives, but Duff procedure (with hexamethylenetetramine in trifluoroacetic acid) gives a possibility to obtain the target pseudo aromatic aldehyde with the 69% yield. Convenient precursors for [4 + 2]- or [3 + 2]-cycloaddition reactions are obtained by means of condensation of synthesized 3-N-methyl-9-formylcytisine with acetone, nitromethane and phosphorous ylides with yields from 70 to 87%. Alternative aprroach to alkenyl products and to 9-alkynyl-3-methylcytisine is realized using the Heck and Sonogashira cross-coupling reactions of methyl vinyl ketone, cyclohexenone or trimethylsilylacetylene with 9-bromo-3-methylcytisine (55, 70 and 60% accordingly). It is shown, that interaction of 3-N-methyl-9-formylcytisine with hydroxylamines leads to corresponding nitrone (93%) and oxime (70%). All individual compounds are isolated by column chromatography and completely characterized on the basis of NMR spectroscopy data.