Novel tricomponent membranes containing poly(ethylene glycol)/poly(pentamethylcyclopentasiloxane)/poly(dimethylsiloxane) domains

The synthesis and characterization of novel tricomponent networks consisting of well‐defined poly(ethylene glycol) (PEG) and poly(dimethylsiloxane) (PDMS) strands crosslinked and reinforced by poly(pentamethylcyclopentasiloxane) (PD₅) domains are described. Network synthesis occurred by dissolving α,ω‐diallyl PEG and α,ω‐divinyl PDMS prepolymers in a common solvent (toluene), introducing a stoichiometric excess of pentamethylcyclopentasiloxane (D₅H) to the charge, inducing the cohydrosilation of the prepolymers by Karstedt's catalyst and completing network formation by the addition of water. Water in the presence of the Pt‐based catalyst oxidizes the SiH groups of D₅H to SiOH functions that immediately polycondense and bring about crosslinking. The progress of cohydrosilation and polycondensation was followed by monitoring the disappearance of the SiH and SiOH functions by Fourier transform infrared spectroscopy. Because cohydrosilation and polycondensation are essentially quantitative, overall network composition can be controlled by calculating the stoichiometry of the three network constituents. The very low quantities of extractable (sol) fractions corroborate efficient crosslinking. The networks swell in both water and hexanes. Differential scanning calorimetry showed three thermal transitions assigned, respectively, to PEG (melting temperature: 46–60 °C depending on composition), PDMS [glass‐transition temperature (T_g) = ～?121 °C], and PD₅ (T_g = ～?159 °C) and indicated a phase‐separated tricomponent nanoarchitecture. The low T_g of the PD₅ phase is unprecedented. The strength and elongation of PEG/PD₅/PDMS networks can be controlled by overall network composition. The synthesis of networks exhibiting sufficient mechanical properties (tensile stress: 2–5 MPa, elongation: 100–800%) for various possible applications has been demonstrated. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3093–3102, 2002     

Synthesis and characterization of model polybutadiene‐1,4‐b‐polydimethylsiloxane‐b‐polybutadiene‐1,4 copolymers

Model copolymers of poly(butadiene) (PB) and poly(dimethylsiloxane) (PDMS), PB‐b‐PDMS‐b‐PB, were synthesized by sequential anionic polymerization (high vacuum techniques) of 1,3‐butadiene and hexamethylciclotrisiloxane (D₃) on sec‐BuLi followed by chlorosilane‐coupling chemistry. The synthesized copolymers were characterized by nuclear magnetic resonance (¹H NMR), size‐exclusion chromatography (SEC), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). SEC and ¹H NMR results showed low polydispersity indexes (M_w/M_n) and variable siloxane compositions, whereas DSC and TGA experiments indicated that the thermal stability of the triblock copolymers depends on the PDMS composition. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2726–2733, 2007     

Networks and conetworks of PIB‐based cyanoacrylate‐telechelic prepolymers: Synthesis,characterization, and properties

Novel networks and conetworks were prepared by the instantaneous polymerization of cyanoacrylate‐telechelic three‐arm star polyisobutylene [Ø(PIB‐CA)₃] and the copolymerization of Ø(PIB‐CA)₃/2,4,4‐trimethylpentane cyanoacrylate (TMP‐CA) mixtures, respectively, by means of strong nucleophiles, such as NEt₂‐telechleic linear or three‐arm star PIBs [Ø(PIB‐NEt₂)_{2 or 3}]. The reactants were combined in the bulk in double‐barrel syringes by reaction injection molding (RIM). The chemical and mechanical properties of products prepared in the bulk and by conventional solution techniques were characterized by various techniques (swelling, extractables, FTIR and NMR spectroscopies, Instron, microhardness, oxidative resistance, DSC, DMTA). Conditions for the preparation of rubbery materials for possible biomedical applications were developed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2612–2623, 2008     

Novel tricontinuous hydrophilic–lipophilic–oxyphilic membranes: Synthesis and characterization

Novel tricontinuous membranes consisting of well‐defined hydrophilic poly(ethylene glycol) (PEG) and lipophilic polyisobutylene (PIB) segments crosslinked by oxyphilic poly(pentamethylcyclopentasiloxane) (PD₅) domains have been synthesized and characterized. Tricontinuity arises because the three membrane constituents—PEG, PIB, and PD₅—are mutually incompatible and give rise to three independent cocontinuous phases (channels). The continuous PEG segments impart swelling in water (hydrogel character), the rubbery PIB moieties provide strength, and the PD₅ domains provide crosslinking and enhanced O₂ permeability. The synthesis involves the random cohydrosilation of various lengths (number‐average molecular weights) of α,ω‐diallyl‐PEG and α,ω‐diallyl‐PIB segments by pentamethylcyclopentasiloxane (D₅H) followed by water‐mediated oxidation of the SiH groups of the D₅H to SiOH groups, which immediately polycondense to PD₅ domains. Membranes containing about equal amounts of PEG, PIB, and PD₅ give rise to tricontinuous morphologies that allow the simultaneous permeation of water, heptane, and oxygen via three cocontinuous channels. The number‐average molecular weight of the PEG segment, that is, the number‐average molecular weight of the hydrophilic segment between two PD₅ crosslink sites, determines the dimensions (pore sizes) of the channels through which water can permeate. A method has been developed for studying the oxygen permeability of membranes. The microarchitecture of the membranes has been investigated with selective swelling experiments and Fourier transform infrared spectroscopy, their mechanical properties have been examined in the water‐swollen state with Instron measurements, and their bulk morphologies and thermal degradation have been determined with differential scanning calorimetry and thermogravimetric analysis, respectively. The findings have been interpreted in terms of phase‐separated PEG, PIB, and PD₅ microdomains. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1209–1217, 2002     

Synthesis and characterization of model diblock copolymers of poly(dimethylsiloxane) with poly(1,4‐butadiene) or poly(ethylene)

Model diblock copolymers of poly(1,4‐butadiene) (PB) and poly(dimethylsiloxane) (PDMS), PB‐b‐PDMS, were synthesized by the sequential anionic polymerization (high vacuum techniques) of butadiene and hexamethylciclotrisiloxane (D₃) in the presence of sec‐BuLi. By homogeneous hydrogenation of PB‐b‐PDMS, the corresponding poly(ethylene) and poly(dimethylsiloxane) block copolymers, PE‐b‐PDMS, were obtained. The synthesized block copolymers were characterized by nuclear magnetic resonance (¹H and ¹³C NMR), size‐exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and rheology. SEC combined with ¹H NMR analysis indicates that the polydispersity index of the samples (M_w/M_n) is low, and that the chemical composition of the copolymers varies from low to medium PDMS content. According to DSC and TGA experiments, the thermal stability of these block copolymers depends on the PDMS content, whereas TEM analysis reveals ordered arrangements of the microphases. The morphologies observed vary from spherical and cylindrical to lamellar domains. This ordered state (even at high temperatures) was further confirmed by small‐amplitude oscillatory shear flow tests. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1579–1590, 2006     

PVA networks grafted with PDMS branches

We describe a simple and efficient synthesis of poly(vinyl alcohol) (PVA) networks fitted with polydimethylsiloxane (PDMS) branches (PVA_netw‐g‐PDMS). The syntheses were achieved in two steps: (1) Grafting by urethane linking PDMS carrying ? NCO termini (PDMS‐NCO) onto PVA fitted with a few (～4) photoreactive acryl amide groups (PVA_AA), followed by (2) Photocrosslinking the PVA_AA‐g‐PDMS to PVA_netw‐g‐PDMS. The use of the binary N‐methyl‐2‐pyrrolidone/tetrahydrofuran (NMP/THF, 67/33) solvent system enabled the thermodynamically unfavorable mixing of hydrophobic PDMS branches with hydrophilic PVA_AA backbones. The amphiphilic graft, PVA_AA‐g‐PDMS, was characterized by ¹H NMR spectroscopy, and the final graft network, PVA_netw‐g‐PDMS, by FTIR spectroscopy, DSC, and equilibrium swelling. The grafting of sufficient volumes of PDMS branches onto PVA_AA yields cocontinuous hydrophilic/hydrophobic PVA/PDMS domains, whose existence was demonstrated by swelling in both water and hexanes. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5272–5277, 2009     

Ideal tetrafunctional amphiphilic PEG/PDMS conetworks by a dual‐purpose extender/crosslinker. II. Characterization and properties of water‐swollen membranes

Select characteristics and properties of a series of ideal tetrafunctional amphiphilic conetworks consisting of random poly(ethylene glycol) (PEG) and polydimethylsiloxane (PDMS) segments crosslinked by a novel dual‐purpose crosslinker/extender were determined. The overall composition of the conetworks was varied in the 16–40% PEG range, and membranes were prepared by polymerizing/crosslinking charges in molds. Membranes were characterized by equilibrium swelling (both in water and n‐heptane) and by determining their oxygen permeabilities and select mechanical properties. Swelling in water increases, whereas in heptane it decreases with increasing PEG content. Significant swelling in both solvents indicates bicontinuous (bipercolating) PEG and PDMS phases. Bicontinuity is reached with ～13% PEG in the conetworks. The oxygen permeabilities of optically clear water‐swollen membranes containing 24, 32, and 40 wt % PEG are ～350, ～245 and ～185 barrers, respectively, i.e., oxygen permeability decreases by increasing the hydrophilic constituent. These oxygen permeabilities are far superior to those of contemporary soft contact lenses. The tensile strengths and moduli of water‐swollen membranes decrease, while elongations increase, with increasing PEG content. Dry membranes exhibit first order transitions at ?52 and ～46 °C indicating phase‐separated crystalline PDMS and PEG domains, respectively. Both dry and water‐swollen membranes are optically clear, indicating the presence of PEG and PDMS domains with dimensions well below the wavelength of visible light. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4965–4971, 2005     

Synthesis of well‐defined star‐shaped poly(ε‐caprolactone)/poly(ethylbene glycol) amphiphilic conetworks by combination of ring opening polymerization and “click” chemistry

Well‐defined star‐shaped hydrophobic poly(ε‐caprolactone) (PCL) and hydrophilic poly(ethylene glycol) (PEG) amphiphilic conetworks (APCNs) have been synthesized via the combination of ring opening polymerization (ROP) and click chemistry. Alkyne‐terminated six arm star‐shaped PCL (6‐s‐PCLx‐C?CH) and azido‐terminated PEG (N₃‐PEG‐N₃) are characterized by ¹H NMR and FT‐IR. The swelling degree of the APCNs is determined both in water and organic solvent. This unique property of the conetworks is dependent on the nanophase separation of hydrophilic and hydrophobic phases. The morphology and thermal behaviors of the APCNs are investigated by SEM and DSC respectively. The biocompatibility is determined by water soluble tetrazolium salt reagents (WST‐1) assay, which shows the new polymer networks had good biocompatibility. Through in vitro release of paclitaxel (PTX) and doxorubicin (DOX), the APCNs is confirmed to be promising drug depot materials for sustained hydrophobic and hydrophilic drugs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 407–417     

Preparation of three‐dimensional poly(dimethylsiloxane) (PDMS) with movable cross‐linking

A pentamethylcyclotrisiloxane moiety was introduced into cyclic polystyrene (cPSt) and cyclic PDMS (cPDMS) to obtain noncovalent cross‐linking agents, D₃‐cPSt and D₃‐cPDMS, respectively. Anionic ring‐opening polymerization of octamethylcyclotetrasiloxane (D₄) in nitrobenzene was carried out in the presence of D₃‐cPSt to obtain a cloudy white PDMS gel as a precipitation. On the other hand, bulk copolymerization of D₃‐cPDMS with D₄ proceeded in a homogeneous state to give a colorless transparent PDMS gel in high yield. The formation of mechanically linked PDMS with movable cross‐linking was indicated by control experiment. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5882–5890, 2009     

Cyclolinear polysiloxanes. II. Crosslinking and characterization

The synthesis and characterization of two groups of novel networks prepared from cyclolinear polysiloxanes are described. The first group of networks from cyclolinear polysiloxanes (N‐CLPSs) was synthesized by the hydrosilation of vinyl‐terminated cyclolinear polyorganosiloxanes [prepared from diacetoxydiethyltetramethylcyclotetrasiloxane (D₄Et₂OAc₂) or diacetoxytriethylpentamethylcyclopentasiloxane (D₅Et₃OAc₂)] with a copolymer of dimethylsiloxane and methylhydrosiloxane as the crosslinking agent. Hydrosilation was effected with a platinum carbonyl catalyst with a cyclovinylsiloxane moderator. The second group of networks (N‐eCLPSs) was prepared similarly with extended cyclolinear polysiloxanes. The mechanical properties of the novel networks were comparable to those of polydimethylsiloxane networks (N‐PDMS). The oxygen permeabilities were similar to or slightly higher than that of N‐PDMS. The glass‐transition temperatures of D₄Et₂OAc₂‐ and D₅Et₃OAc₂‐based N‐CLPSs were ?67.8 and ?90.8 °C, respectively, whereas the incorporation of polydimethylsiloxane spacers into similar N‐eCLPSs lowered their glass‐transition temperatures to ?109.7 and ?115.0 °C. Upon heating to 800 °C in air, N‐CLPSs yielded more residue than N‐eCLPSs, which in turn yielded more residue than N‐PDMS. These results may have been due to the presence of T units in the cyclic siloxane units, which may have inhibited chain degradation or the formation of volatile products. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4053–4062, 2006     

Poly(pentamethylcyclopentasiloxane). I. Synthesis and characterization

We have discovered that pentamethylcyclopentasiloxane (D₅H) can be readily polymerized into poly(pentmethylcyclopentasiloxane) (PD₅) with a Pt (Karstedt) catalyst in the presence of water in bulk or in solution at 100 °C and that the product is a solid with extraordinary properties. The polymerization starts with the oxidation of the SiH groups by water into an intermediate containing SiOH groups (SiH + H₂O → SiOH + H₂), which is followed immediately by the condensation (2SiO → Si? O? Si) of D₅H rings into complex aggregates of cyclosiloxane moieties. According to Raman spectroscopy, an average of three of the five SiH functionalities are converted, and the final product contains only a negligible number of SiOH groups. The melting and glass‐transition temperatures of the monomer are exceptionally low: T_m,D5H = ?137.6 ± 1 and T_g,D5H = ?152 ± 2 °C. The polymer exhibits an unprecedented combination of properties: it is a stiff and brittle solid, is insoluble in common solvents, does not exhibit a melting endotherm but has an extremely low glass transition (T_g,PD5 = ?151 ± 0.5 °C), and is thermally stable up to at least 700 °C. Brillouin scattering indicates very slow variation of the relaxation time with temperature, a property characteristic of strong glass‐forming systems such as silica glass. This characteristic may account for the unique combination of properties of the new polymer: an extremely low glass‐transition temperature combined with solidlike properties even at ambient temperature (more than twice its glass‐transition temperature). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1285–1292, 2002     

Novel amphiphilic triblocks fitted with photocrosslinkable termini,and their photocrosslinking to conetworks

Two new telechelic amphiphilic triblock copolymers, HE₃‐PEG‐b‐PDMS‐b‐PEG‐HE₃ and HE₃‐PEG‐b‐PDMS‐b‐PEG‐HE₃, i.e., sequence‐reversed triblocks of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic polydimethylsiloxane (PDMS) segments fitted with photocrosslinkable tri[2‐(3,4‐cyclohexane oxide)ethyl‐dimethylsiloxy]silane (HE₃) termini, were synthesized, characterized, photocrosslinked to amphiphilic conetworks (APCNs), and the properties of the APCNs were analyzed. APCNs in which the crosslinking sites are located in the hydrophobic domains exhibited significantly better mechanical properties than those in which the crosslinks were in the hydrophilic domains. The stiff domains formed of the UV‐crosslinkable HE₃ chain‐end substituents provide not only crosslinking but reinforcement as well. The crosslinking/reinforcement efficiency was greatly enhanced by the addition of excess HE₃. Water‐swollen APCNs were optically clear and exhibited mechanical properties appropriate for biomedical application. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 174–185, 2008     

Third‐generation amphiphilic conetworks. III. Permeabilities and mechanical properties

While two of our earlier papers on poly(dimethyl acryl amide)/polymethylhydrosiloxane/polydimethylsiloxane (PDMAAm/PMHS/PDMS) amphiphilic conetworks concerned synthesis and biological properties, respectively, the present contribution focuses on oxygen and insulin permeabilities, and select mechanical properties. We show that by increasing the PDMAAm content from 20 to 60% (i.e., by decreasing the hydrophobic content from 80 to 40%), oxygen permeabilities decrease from ～240 to ～130 barrers. Evidently, oxygen permeability is a function of the sum of the oxyphilic components, PDMS + PMHS, in the conetworks. In contrast, insulin permeability is a function of the hydrophilic component, and reaches a desirable 1.5 × 10^?7 cm²/s at 61% PDMAAm. We also studied the permeabilities of glucose, dextran, and albumin through a PDMAAm₆₁/PMHS₆/PDMS₃₃ membrane and found, unsurprisingly, that the permeability of these molecules follows their hydrodynamic radii, and we project that the permeability of IgG is infinitesimally low. Tensile strengths and ultimate elongations of water‐swollen membranes are also a function of conetwork composition: by increasing the PDMAAm content from 30 to 60%, strengths decrease from 1.6 to 1.2 MPa, and elongations from ～60 to ～40%. Overall, the permeabilities and the mechanical properties of these membranes are appropriate for implantation and, specifically, for immunoisolation of living tissue. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4276–4283, 2007     

Synthesis and characterization of model 3‐miktoarm star copolymers of poly(dimethylsiloxane) and poly(2‐vinylpyridine)

3‐Miktoarm star copolymers, 3μ‐D₂V, with two poly(dimethylsiloxane) (PDMS) and one poly(2‐vinylpyridine) (P2VP) arm, were synthesized by using anionic polymerization–high vacuum techniques and (chloromethylphenylethyl)methyl dichlorosilane, heterofunctional linking agent, with two SiCl groups and one CH₂Cl group. The synthetic strategy involves the selective reaction of the two ? SiCl groups with PDMSOLi living chains, followed by reaction of the remaining chloromethyl group with P2VPLi. Combined molecular characterization results (size exclusion chromatography, membrane osmometry, and ¹H NMR spectroscopy) revealed a high degree of structural and compositional homogeneity. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 614–619, 2006     

Amphiphilic membranes crosslinked and reinforced by POSS

This article concerns the synthesis and characterization of novel tricomponent amphiphilic membranes consisting of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic polydimethylsiloxane (PDMS) segments cocrosslinked and reinforced by octasilane polyhedral oligomeric silsesquioxane (octasilane‐POSS) cages. Rapid and efficient network synthesis was effected by cocrosslinking diallyl‐telechelic PEG (A‐PEG‐A) and divinyl‐telechelic PDMS (V‐PDMS‐V) with pentamethylpentacyclosiloxane (D₅H), using Karstedt's catalyst in conjunction with Et₃N cocatalyst and water. Films were prepared by pouring charges in molds and crosslinking by heating at 60 °C for several hours. The films were characterized by sol fractions and equilibrium swelling both in hexane and water, extent of crosslinking, contact angle hysteresis, oxygen permeability, thermogravimetric analysis, and mechanical properties. The crosslinking of octasilane‐POSS achieved by the same catalyst system was studied in separate experiments. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4337–4352, 2004     

Phenol‐urea‐formaldehyde cocondensed resol resins: Their synthesis,curing kinetics,and network properties

Several phenol‐urea‐formaldehyde (PUF) cocondensed resol resins were synthesized by different procedures. The curing kinetics and network properties of these PUF resins were examined by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). A kinetic study indicated that the activation energy values of PUF resins are generally higher than those of phenol‐formaldehyde (PF) resins during curing processes, but the curing rates of PUF resins are faster than those of PF resins. The pH values of PUF systems have a significant influence on the rate constants, although they affect the activation energy very slightly. Moreover, the dependence of activation energy on the conversion showed that there are more individual reactions with different activation energies occurring during the curing processes in PUF resins than in PF resins. The decomposition of methylene ether bridges to form methylene bridges probably occurs at high temperature in PUF resins. DMTA data indicated that the network rigidity of PUF resins is slightly lower than that of PF resin. The gel point and T_{tan δ2} transition measured by DMTA were consistent with the kinetic results obtained from the DSC data, but they were also related to the physical and mechanical properties of the network, especially with regard to the T_{tan δ2} transition. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1929–1938, 2003     

Polymerizability,copolymerizability, and properties of cyanoacrylate‐telechelic polyisobutylenes II: copolymerization of three‐arm star cyanoacrylate‐ telechelic polyisobutylene with ethyl cyanoacrylate

This research concerned the synthesis and characterization of novel conetworks containing polyisobutylene (PIB) and polyethyl‐2‐cyanoacrylate [poly(Et‐CA)] sequences. The syntheses involved the copolymerization of CA‐telechelic three‐arm star PIB [Ø(PIB‐CA)₃] with ethyl‐2‐cyanoacrylate (Et‐CA) mediated by nucleophiles or by living tissue (fresh eggs). The conetworks were characterized by swelling in hexanes, tetrahydrofuran (THF), and acetone, and the results indicate co‐continuous PIB and poly(Et‐CA) domains. The conetworks exhibit two T_gs indicating phase‐separation between PIB and poly(Et‐CA). The outstanding oxidative resistance of the conetworks was demonstrated by exposure to concentrated nitric acid. The tensile strengths, moduli, and elongations of a series of conetworks with different overall compositions were investigated and the findings interpreted in terms of covalently linked rubbery and glassy domains. AFM also suggests the presence of phase‐separated rubbery and glassy domains. DMTA spectra of a Ø(PIB‐CA)₃ homonetwork, and Ø(PIB‐CA)₃/Et‐CA conetworks were analyzed and interpreted in terms of coexisting rubbery and glassy domains. Observations made during the exposure of Ø(PIB‐CA)₃/Et‐CA mixtures to proteinaceous tissue, in combination with characterization data, were used to propose a structural model for the conetworks. Copyright © 2007 John Wiley & Sons, Ltd.     

Novel silicon‐containing spiroorthoester to confer combined flame retardancy and low shrinkage properties to epoxy resins

A new silicon‐containing spiroorthoester, 1,4,6‐trioxaspiro [4,4]‐2‐nonylmethyl 3‐trimethylsilyl propionate (SOE? Si), was synthesized with good yield by an esterification reaction with a previously synthesized 2‐hydroxymethyl‐1,4,6‐trioxaspiro [4,4] nonane (SOE? OH) and trimethylsilyl propionic acid. The structure of the new SOE? Si was confirmed by ¹H and ³C NMR. The SOE? Si and a mixture of DGEBA/SOE? Si were polymerized with ytterbium triflate as a cationic initiator. The curing was studied with differential scanning calorimetry (DSC) and monitored by Fourier transform infrared (FTIR) spectroscopy. The materials were characterized with DSC, termogravimetric analysis (TGA) and thermodynamomechanical analysis (DMTA). The volume change was evaluated with a Micromeritics gas pycnometer and the flame retardancy was tested by the limiting oxygen index (LOI) measurements. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4211–4224, 2007     

Ideal tetrafunctional amphiphilic PEG/PDMS conetworks by a dual‐purpose extender/crosslinker. I. Synthesis

The synthesis of a new type of amphiphilic conetwork (APCN) consisting of well‐defined hydrophilic poly(ethylene glycol) (PEG) and hydrophobic polydimethylsiloxane (PDMS) segments is described. The conetwork is ideal (the lengths of each PEG and PDMS chain segments, respectively, are identical) and tetrafunctional (exactly four chains emanate from each crosslink site). The synthesis of the conetworks was achieved by the use of a novel dual‐purpose extender/crosslinker Y (bis [(dimethylsilyl)oxy]‐[(etoxydimethylsilyl)oxy]phenylsilane, (SiPh(SiH)₂OEt)), in two steps: (1) Synthesis of a new linear random multiblock copolymer (MBC) (AY)_n(BY)_m, where A is the hydrophilic PEG and B is the hydrophobic segment, and (2) Crosslinking the multiblocks by catalytic condensation of the SiOEt groups in the Y units. The extender/crosslinker fulfills two totally different functions: First, it extends two incompatible hydrophilic and hydrophobic prepolymers (PEG and PDMS) to a random MBC, and, subsequently, it cross‐links the multiblocks to the target APCN. The synthesis and characterization of the extender/crosslinker is also presented. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4953–4964, 2005     

Characterization of plasma polymers from tetramethylsilane,octamethylcyclotetrasiloxane, and methyltrimethoxysilane

The products in inductively coupled plasma excited in organosilicic compounds were studied on chemical structures by spectroscopic methods. Plasma-polymerized tetramethylsilane (PA) contains not only Si? CH₃ groups but also Si? H groups on IR and ²⁹Si-NMR analyses. ¹³C-NMR spectrum of PA reveals that the crosslinked structure of PA is mainly constructed of Ch₂ and CH groups. Plasma-polymerized octamethyleyclotetrasiloxane (PD₄) is composed of Si? CH₃ and Si? O groups. ¹³C- and ²⁹Si-NMR spectra of PD₄ point out the highly preservation of the structural units similar to the monomer. These data of PD₄ suggest that PD₄ is formed from the ring-opening polymerization by cleavages of Si? O bonds. ¹³C-NMR spectrum of poly[methyltrimethoxysilane] (PT) indicates the existence of CH₃? O groups, meanwhile its ²⁹Si-NMR analysis concludes that PT is chiefly composed of the structural units similar to the monomer. The surface analyses by XPS of PA, PD₄ and PT suggest that these organosilicic plasma polymers resemble their starting materials.