Synthesis and characterization of photosensitive benzocyclobutene‐functionalized siloxane thermosets

Two methylphenylsiloxane monomers with crosslinkable benzocyclobutene functionalities at the terminal positions, 1,1,5,5‐dimethyldiphenyl‐1,1,5,5‐di[2′‐(4′‐benzocyclobutenyl)vinyl]‐3,3‐diphenyltrisiloxane (BCB‐1) and 1,1,3,3‐dimethyl‐diphenyl‐1,1,3,3‐di[2′‐(4′‐benzocyclobutenyl)vinyl]disiloxane (BCB‐2) were prepared and characterized. By heating the solution of BCB‐1 and BCB‐2 in mesitylene, two partially polymerized resins of BCB‐1B and BCB‐2B with high molecular weight were also achieved. The monomers and their oligomers fully cured at temperatures above 250 °C. Cured BCB‐1 and BCB‐2 exhibited high T_g (257 and 383 °C) and good thermal stability (T_5% > 472 °C both in N₂ and in air). They also demonstrated low dielectric constants (2.69 and 2.66), low dissipation factors (2.36 and 2.23), and low water absorptions (0.20% and 0.17%). Moreover, a negative photosensitive formulation derived from BCB‐1B in combination with 2,6‐bis(4‐azidobenzylidene)‐4‐methylcyclohexanone (BAC‐M) as a photosensitive agent has been developed. The photosensitive composition, BCB‐1B containing 5 wt % BAC‐M, showed a sensitivity of 550 mJ/cm² and a contrast of 1.96 when it was exposed to a 365 nm light (i‐line) and developed with cyclohexanone at 25 °C. A fine negative image of 10 μm line‐and‐space pattern was also printed in a film which was exposed to 700 mJ/cm² of i‐line by contact‐printing mode. The negative image can be maintained without any pattern deformation in the curing process. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6246–6258, 2009     

Benzoxazine-epoxy thermosets with smectic phase structures for high thermal conductive materials

ABSTRACT

To further increase the intrinsic thermal conductivity (TC) of polybenzoxazine, a series of benzoxazine-epoxy thermosets (s-PBEI) were obtained through the sequential curing of a smectic phase epoxy monomer (s-EP) and a bifunctional benzoxazine monomer (BZ) in the presence of imidazole. The results show that s-PBEI exhibits a smectic mesophase. The formation mechanism of the smectic phase is reaction-induced phase separation caused by the preferential curing of s-EP. Owing to the increment of the liquid crystalline structure content, the TC of s-PBEI increases with increasing s-EP content. The TC of s-PBEI55 containing equal weight of BZ and s-EP reaches 0.30 W m^?1 K^?1, which is higher than that of n-PBEI55, a benzoxazine-epoxy thermoset with nematic phase structures. Additionally, the TC, glass transition temperature, and 10% weight loss temperature of s-PBEI64 containing 60 wt% BZ and 40 wt% s-EP are 0.28 W m^?1 K^?1, 216°C, and 334°C, respectively, indicating its potential applications in electronic packaging, LED lighting, and other fields requiring a high TC resin matrix.     

Preparation of high molecular weight polybenzoxazine prepolymers containing siloxane unites and properties of their thermosets

High‐molecular‐weight polybenzoxazine prepolymers containing polydimethylsiloane unit in the main‐chain have been synthesized from α,ω‐bis(aminopropyl)polydimethylsiloxane (PDMS) (molecular weight = 248, 850, and 1622) and bisphenol‐A with formaldehyde. Moreover, another type of prepolymers was prepared using methylenedianiline (MDA) as codiamine with PDMS. The weight average molecular weight of the obtained prepolymers was estimated from size exclusion chromatography to be in the range of 8000–11,000. The chemical structures of the prepolymers were investigated by ¹H NMR and IR analyses. The prepolymers gave transparent free standing films by casting their dioxane solution. The prepolymer films after thermally cured up to 240 °C gave brown colored transparent and flexible polybenzoxazine films. Tensile test of the films revealed that the elongation at break increased with increasing the molecular weight of PDMS unit. Dynamic mechanical analysis of the thermosets showed that the T_gs were as high as 238–270 °C. The thermosets also revealed high thermal stability as evidenced by the 5% weight loss temperatures in the range of 324–384 °C from thermogravimetic analysis. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Yttrium thiocyanate-based supramolecular architectures: Synthesis, crystal structures, and thermal properties

The reaction of [Y(H₂O)₅(NCS)₃]·H₂O (1) with crown ether (18-crown-6) and KNCS in methanol afforded the complexes [Y(H₂O)₄(NCS)₃]·1.5(18-crown-6) (2) and [K(18-crown-6)(H₂O)_1.25]_2n{[K(18-crown-6)]₂[Y(NCS)₆]}_n·n(NCS) (3). In mononuclear complex 1, yttrium has a coordination number 8 and forms the coordination unit YO₅N₃. Complexes 1 are linked by hydrogen bonds to form a framework. The crystal structure of 2 contains the centrosymmetric ensembles [Y(H₂O)₄(NCS)₃]₂(18-crown-6)₃ formed via hydrogen bonds. In the crystal structure of 3, the [Y(NCS)₆]³⁻ anions and the [K(18-crown-6)]⁺ cations form one-dimensional polymeric chains (-Y-NCS-K-)_n. The thermal behavior of compounds 1 and 2 was investigated. It was shown that the supramolecular assembly has an effect on the temperature range for the removal of coordinated water molecules from the thiocyanate complex. The oxidative decomposition of the acido ligands in 1 and 2 occurs in a similar way to give Y₂O₂SO₄ as the final product (700 °С).     

Influence of siloxane co-segment length and content of waterborne polysiloxane-urethane copolymers on their water resistance, thermal stability and mechanical properties

<正>A series of stable waterborne polysiloxaneurethane(WPSUR) dispersions were prepared using amino-terminated polydimethylsiloxane(NS),dimethylolpropionic acid(DMPA),castor oil,polypropylene glycol and toluene diisocyanate. Meanwhile,NS with different molecular weights was synthesized and used as the soft co-segment.Effects of types and contents of soft co-segments as well as chain extenders on the thermal degradation and stability for WPSUR films were examined.Results reveal that WPSUR films exhibit excellent water resistance and mechanical properties as compared with pure polyurethane(PU) films,and the NS soft co-segment possesses a remarkable effect on the second stage(stageⅡ),while the content of the hard segment is propitious to the initial stage(stageⅠ).Moreover,the highest temperature of stageⅡ(T_(2m)) for WPSUR films using NS as soft co-segment is 413℃,approximately being 30℃higher than that of those typical PUs using HDA and APDMS as the chain extenders,respectively.     

Synthesis,characterization, and mechanical properties of PMMA/poly(aromatic/aliphatic siloxane) semi-interpenetrating polymer networks

Semi-interpenetrating polymer networks (IPNs) composed of poly(methyl methacrylate) (PMMA) and aromatic/aliphatic siloxanes have been made via sequential and simultaneous polymerizations. As the percentage of aliphatic siloxane increases, flexibility and, in general, toughness of the IPNs increases and clarity is reduced. This loss in clarity is due to the mismatch of refractive indices (1.49 form PMMA vs. 1.43 for aliphatic siloxane). PMMA is quite transparent. On the other hand, in making aromatic siloxane/PMMA IPNs clarity is retained as aromatic siloxane is increased due to better matching refractive index (1.49 for PMMA and −1.49 for poly(diphenyl siloxane)). Gel permeation chromatography (GPC) indicates slightly crosslinked IPNs with the THF soluble portions having number-average molecular weight, M¯_n, of 10⁵–10⁶. NMRs of IPNs essentially show peaks for the components, PMMA and the siloxane, which make up the respective IPNs. ²⁹Si-NMRs indicate cross-linking and grafting. Mechanical properties show increased toughness of IPNs versus PMMA as percentage of siloxane and crosslinker increases, but with a corresponding loss in tensile strength. © 1996 John Wiley & Sons, Inc.     

Synthesis,crystal structures,thermal properties,and DNA-binding studies of transition metal complexes with imidazole ligands

A new series of complexes of transition metal (Cu, Zn, Ni) perchlorate with imidazole have been synthesized and characterized by elemental analysis, infrared (IR), UV-Vis spectroscopy, and single-crystal X-ray diffraction. Based on elemental and spectral data, the complexes are M(C₃H₄N₂) _x (ClO₄)₂ (M?=?Cu, Zn, x?=?4; M?=?Ni, x?=?6; C₃H₄N₂?=?imidazole). The crystal structures of Cu(C₃H₄N₂)₄(ClO₄)₂ (1) and Zn(C₃H₄N₂)₄(ClO₄)₂ (2) show metals surrounded by four nitrogens of imidazole, while the nickel complex Ni(C₃H₄N₂)₆(ClO₄)₂ (3) has six nitrogens of imidazole. Intra- and inter-molecular hydrogen bonds exist between hydrogen of imidazole and oxygen of perchlorate. The thermal stabilities of 1, 2, and 3 at different heating rates (β?=?5°C?min^?1, 10°C?min^?1, and 15°C?min^?1) show that all the complexes exhibit two thermal decomposition stages; the sequence of thermal stability is 2?>?1?>?3. 1, 2, 3, and imidazole display DNA binding ability, ascertained by UV-Vis titration.     

Effect of different polyethers on surface and thermal properties of poly(urethane-siloxane) copolymers modified with side-chain siloxane

Poly(urethane-dimethylsiloxane) (PU-PDMS) copolymers with 4,4′-methylenebis(cyclohexyl isocyanate), different polyethers i.e., poly(oxytetramethylene)diol, poly(ethylene glycol), poly(propylene glycol), and α,ω-dihydroxy terminated polydimethylsiloxane extended with 1,4-butanediol in two-step solution polymerization were obtained. The PU-PDMS were modified using 1.25 mol% of polydimethylsiloxane which was incorporated into main polyurethane backbone as a side chain. The structure of the synthesized PU-PDMS was confirmed by FTIR as well as ¹H and ¹³C-NMR spectroscopy. The effect of different soft segments on free surface energy (FSE) components and thermal stability of poly(urethane-siloxane) copolymers was investigated. The activation energy of the thermal degradation of PU-PDMS using isoconversional methods (Ozawa–Flynn–Wall and Friedman) was calculated. It was concluded that molecular mass, thermal stability, and FSE of PU-PDMS copolymers depend on polyol used. The apparent activation energy at first step of degradation in nitrogen generally increases with the extent of conversion which may result from complex mechanism related to formation of decomposition products. Hydrophobic character of side-chain siloxane on surface properties of the PU-PDMS coatings was confirmed. The obtained coatings are generally soft with the relative hardness in the range of 0.120–0.027.     

Synthesis, growth, thermal, optical and mechanical properties of 2-Aminopyridinium 4-methylbenzoate Dihydrate

Organic NLO material of 2-Aminopyridinium 4-methylbenzoate Dihydrate (2A4M) was synthesized using 2-Aminopyridinium and 4-methylbenzoic acid as starting materials. Single crystals of 2A4M were grown by the slow evaporation solution growth technique at room temperature using water as a solvent. The grown crystal was characterized by single crystal XRD to confirm the crystal system and lattice parameters. From the optical studies the optical band gap and the refractive index of the material are found to be 2.9 eV and 1.40 at 1200 nm. Functional groups of the crystallised material were confirmed by FTIR vibrational spectrum. Thermal behaviour of the title compound was studied using thermogravimetric (TG) and differential thermal analyses (DTA). The initial weight loss is found up to 125°C, which corresponds to 13.2% i.e. presence of 2 mole of water in the lattice. The grown crystal was subjected to Vickers hardness test and the brittleness index, fracture toughness, yield strength were estimated. The etching studies reveal the growth pattern and dislocations present in the grown crystal. The second harmonic generation (SHG) behaviour of 2A4M was tested by Kurtz-Perry powder technique. The relative SHG efficiency of 2A4M is found to be 3.03 times that of the reference material KDP.     

Flexible electrospun PET/TiO2 nanofibrous structures: Morphology,thermal and mechanical properties

In this study, a solvothermal method was used to synthesize anatase titanium dioxide (TiO₂) nanoparticles in the presence of oleic acid (OA) and oleylamine (OM) as morphology‐directing agents. Functional nanocomposite fibers of poly(ethylene terephtalate) (PET) containing surfactants‐capped TiO₂ nanoparticles were developed by electrospinning technique. The morphology, thermal stability and mechanical properties of PET/TiO₂ nanocomposite mats were investigated as a function of TiO₂ concentration. Morphology investigation showed interesting results in terms of the level of TiO₂ dispersion inside the fibers and the improvement of the quality (smoothness) of the fibers' surface when the synthesized nanorhombic TiO₂ nanoparticles were used compared to a commercial P25 TiO₂ (AEROXIDE P25)_. The presence of OA and OM on the surface of the nanorhombic synthesized TiO₂ led to a significant improvement of TiO₂ dispersion inside the PET matrix. Furthermore, the physical interaction between the PET matrix and TiO₂ nanoparticles resulted in an enhanced thermal stability, and an increase of the Young's modulus and tensile strength for TiO₂ concentration up to 10 wt%.     

Synthesis of polydithiourethanes and their thermal,optical, and mechanical properties originated from monomers structure

Polyaddition of various diisothiocyanates and dithiols was achieved with triethylamine in dimethylformamide at 25 °C for 12 h under nitrogen, and then the corresponding polydithiourethanes (PDTUs) were obtained with high yield and molecular weight without depending on the monomer structures, although the dithiol monomer of the low nucleophilicity was unsuitable for polyaddition in this system. The chemical and physical properties of the obtained PDTUs such as solvent solubility, glass transition temperature, thermal stability, transparency, refractive index, and tensile strength, were analyzed in detail by gel permeation chromatography, nuclear magnetic resonance, Fourier transform infrared–attenuated total reflection, ultraviolet–visible, differential scanning calorimetry, thermogravimetric analysis, and tensile testing measurements. These results proved that PDTUs and their cast films having the aliphatic diisothiocyanate and dithiol moieties exhibited excellent chemical and physical properties compared to that of the aromatic PDTUs. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2255–2262     

The thermal properties of polysiloxanes poly(dimethyl siloxane) and poly(diethyl siloxane)

New measurements and literature data on polysiloxanes covering heat capacities, transition parameters, enthalpies, entropies and Gibbs energies are presented and critically reviewed. TheATHAS computation method is used to bring heat capacities into agreement with an approximate frequency spectrum. The various crystal and mesophases are discussed. TheATHAS (1990) recommended data are as follows: For poly(dimethyl siloxane) the glass transition is at 146 K with an increase in heat capacity of 29.24 J/(K mol). The completely crystalline sample melts at about 219 K with a heat of fusion of 2.75 kJ/mol. For poly(diethyl siloxane) the glass transition is at 135 K with an increase in heat capacity of 34.48 J/(K mol). The completely crystalline sample changes to a condis crystal at 206.7 K with a heat of disordering of 2.72 kJ/mol. The transition to a poorly characterized viscous crystal with thermodynamic properties close to the melt occurs at 282.7 K with an enthalpy of transition of 1.84 kJ/mol. Final fusion occurs at 308.5 K and a small endotherm of about 231 J/mol. Tables of heat capacities, enthalpies, entropies and Gibbs energies are given from 0 K to 550 K.

---

Zusammenfassung Neue Messungen und Literaturangaben von Polysiloxanen über Wärmekapazität, Umwandlungsparameter, Enthalpien, Entropien und Gibbssche Energien werden vorgestellt und kritisch betrachtet. Das Rechenverfahren ATHAS wurde benutzt, um die Wärmekapazitäten mit einem annähernden Frequenzspektrum in Einklang zu bringen. Es wurden die verschiedenen Kristall- und Mesophasen diskutiert. Die von ATHAS (1990) empfohlenen Werte sind wie folgt: Für Poly(dimethylsiloxan) beträgt der Glasumwandlungspunkt 146 K bei Zunahme der Wärmekapazität um 29.24 J/(K.mol). Die vollständing kristalline Probe schmilzt bei etwa 219 K mit einer Schmelzwärme von 2.75 kJ/mol. Für Poly(diethylsiloxan) beträgt der Glasumwandlungspunkt 135 K bei Zunahme der Wärmekapazität um 34.48 J/(K.mol). Die vollständig kristalline Probe wandelt sich bei 206.7 K um, die Fehlordnungswärme beträgt 2.72 kJ/mol. Die Umwandlung in einen wenig verstandenen viskosen Kristall, dessen thermodynamische Eigenschaften denen der Schmelze gleichen, erfolgt bei 282.7 K mit einer Umwandlungsenthalpie von 1.84 kJ/mol. Letztendlich verläuft das Schmelzen bei 308.5 K mit einem kleinen endothermen Effekt von etwa 231 J/mol. Wärmekapazitäten, Enthalpien, Entropien und Gibbssche Energien sind für den Bereich 0 K–550 K tabellarisch angegeben.

---

, , , , . ATHAS , - . . ATHAS (1990) : 146 29,24 / ·. 219 2,75 /. 135 34,48 /·. 206,7 2,72 /. « » 282,7 1,84 /. 308,5 231 /. , , 0–550 .

---

---

This work was supported by the National Science Foundation, Polymers Program, Grant #DMR 83-17097 and early work of J.P.W. was supported by the Am. Chem. Soc. Petroleum Research Found, Grant 12431-AC7. In addition at Oak Ridge National Laboratory the work was sponsored by the Division of Materials Sciences, Office of Basic Energy Sciences, U.S. Department of Energy under contract DE-AC05-84OR21400 with Martin Marietta Energy Systems Inc.     

Synthesis,characterization, and thermal and dielectric properties of three different methacrylate polymers with zwitterionic pendant groups

The synthesis, characterization, thermal, and dielectric properties of three different zwitterionic methacrylates of the sulfobetaine type are presented. Diethylamine-ethyl-, 2-(diethylaminoethoxy)-ethyl-, and 2-(2-diethylaminoethoxy) ethoxy-ethyl-methacrylates were made to react with butanosultone to prepare monomers with variable flexibility. The flexibility of the lateral chain of the polymethacrylates decreased the glass transition temperature (T_g down to 300 K) of the polymers. A linear relationship between T_g and the number of carbon atoms was shown for these materials. X-ray diffraction and DSC experiments showed the formation of new ordered phases in these polymers, which inhibited their dipole conductivity. On heating, these phases were destroyed and values of conductivity of 10⁻⁷–10⁻³ S cm⁻¹ were obtained in the studied range of temperature. Variation of conductivity with temperature was established according to the Arrhenius equation. Dielectric properties exhibited a small deviation of the Debye type behavior, and β parameters of the Cole–Cole equations were calculated for the synthesized polymers. © 1997 John Wiley & Sons, Inc.     

Synthesis, X-ray crystal structures, thermal and electrochemical properties of thiosemicarbazidatodioxouranium(VI) complexes

The stable uranyl complexes, [UO(2)(L)C(9)H(19)OH], were obtained from 3,5-dichlorosalicyl-(L(I)) and salicyl-aldehyde-S-propyl-thiosemicarbazones (L(II)) with substituted-salicylaldehyde in nonyl alcohol. The structures of the complexes have been characterized by elemental analysis, IR, (1)H NMR, conductivity, magnetic moment measurements, cyclic voltammetry, thermal gravimetric analysis and single crystal X-ray diffraction technique. The U(VI) centre is seven-coordinated in a distorted pentagonal bipyramidal geometry. The relative orientations of the nonyl alcohol and S-propyl group in the title complexes are completely different due to different crystal packing. Electrochemical behaviors of the thiosemicarbazone ligands and the uranyl complexes were studied using cyclic voltammetry and square wave voltammetry. Redox processes of the compounds are significantly influenced by the central metal ions and the nature of substituents on the thiosemicarbazones, which are important factors in controlling the redox properties. In situ spectroelectrochemical studies were employed to determine the colors and spectra of electro-generated species of the complexes.     

Physical,thermal and mechanical properties of phenolphthalein polycarbonate

Phenolphthalein polycarbonate, prepared by interfacial polycondensation, was characterized by inherent viscosity measurements, elemental analysis, i.r. spectroscopy, differential scanning calorimetry, differential thermal analysis and thermogravimetric analysis. In addition, the thermal stability of the polycarbonate was evaluated by isothermal gravimetric analysis. Films of the polycarbonate were essentially colourless and showed a high optical transparency since their absorptions in u.v.-visible spectra were in the u.v. range. Tensile properties of the polycarbonate specimens were determined.     

Synthesis of new siloxane urethane block copolymers and their properties

Siloxane urethane block copolymers were prepared with siloxanes as the soft segment. Films were cast from a variety of solvents. Solvent has an effect on the segregation of soft and hard segments. Surface studies, including ESCA, EDS, and FT-IR, show well segregated block copolymers with enhanced siloxane on the surface. DSC studies show a low mp (-44°C) for the soft segment and a T_g for the hard segment above room temperature. These materials show higher thermal stability compared to polyether urethane block copolymers. These copolymers also show relatively good resistance to exposure to oxygen plasma and show improved flame retardancy compared to nonsiliconated, polyether polyurethane block copolymers. © 1994 John Wiley & Sons, Inc.     

Synthesis,structures, and thermal properties of terpolymers of propylene oxide,carbon dioxide,and cyclohexene oxide

High molecular weight block terpolymers with different contents of polypropylene carbonate and cyclohexene carbonate units in the polymer chain were synthesized by the copolymerization of carbon dioxide, propylene oxide, and cyclohexene oxide. Zinc adipate was used as a catalyst. The terpolymerization products were characterized by ¹H and ¹³C NMR spectroscopy, IR spectroscopy, GPC, DSC, and DMA methods. The influence of the reaction conditions on the composition, microstructure, and molecular-weight and thermal characteristics was studied.

     

Polymethyl(hexafluoroalkyl)siloxane Rubbers: Preparation and thermal properties

Polymethyl(hexafluoroalkyl)siloxane rubbers were synthesized by anionic and cationic polymerization of 1,3,5-trimethyl-1,3,5-tris(hexafluoroalkyl)cyclotrisiloxanes and 1,1,3,3,5-pentamethyl-5-(trifluoromethyltri-fluorobicyclo[2.2.1]heptyl)cyclotrisiloxane. The thermal properties of the new fluorosiloxane polymers were studied by thermal gravimetric analysis and differential scanning calorimetry.     

ABS blends with phenoxy: morphology,thermal, mechanical and rheological properties

Blends of ABS (acrylonitrile–butadiene–styrene) with phenoxy(poly(hydroxyether bisphenol A)) were prepared using a Branender single screw extruder. Scanning and transmission electron micrographs (SEM, TEM) showed a typical two-phase morphology; particle-in-matrix (90/10) (ABS/phenoxy by weight), 70/30, 10/90), island/sea (30/70) and co-continuous (50/50) morphologies. The glass transition temperature (T_g) of SAN was almost unchanged in the blends, while the T_g of phenoxy increased by about 5 °C in the blends. The synergistic effect of tensile modulus and strength was noted in ABS-rich blends, where a drastic drop of ductility was seen, and the results were interpreted in terms of rubber particle migration form SAN to phenoxy phase, which was visualized by TEM. Melt viscosity showed yield in ABS-rich blends, and generally followed the log additivity.     

Synthesis,geometric structure,and properties of poly(phenylacetylenes) with bulky para-substituents

Phenylacetylenes (PAs) with bulky substituents (adamantyl, tert-butyl, and n-butyl groups) at the para-position polymerized in good yields with Fe, Rh, Mo, and W catalysts. The formed polymers were soluble, and their number-average molecular weights were in the range of thousands to hundred thousands. Whereas it is known that the poly(PA) obtained with the Fe catalyst is an insoluble cis-cisoidal polymer, the present polymers formed with the same catalyst were totally soluble in many solvents such as benzene and CHCl₃. The ¹H- and ¹³C-NMR and DSC data revealed that both of the polymers formed with the Fe and Rh catalysts had virtually all-cis structures, while those with the Mo and W catalysts had cis-rich and trans-rich structures, respectively. Cis-cisoidal and cis-transoidal structures of para-substituted poly(PAs) could not be distinguished because of their good solubility. The bulky substituents raised the temperature of cis–trans isomerization and improved the thermal stability of the polymers. Poly(p-t-BuPA) showed gas permeability higher than that of poly(PA). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3157–3163, 1998