High refractive index adamantane‐based silicone resins for the encapsulation of light‐emitting diodes

The encapsulation of high power light emitting diode (LED) needs the silicone resins to have relative high refractive index and thermal‐aging properties. Herein, high refractive index adamantane‐based phenyl epoxy‐silicone (APES) resins for LED encapsulation were synthesized by the sol‐gel condensation of 1‐adamantane methanol propyltrimethoxysilane‐3‐urethane, γ‐(2,3‐epoxypropoxy)propytrimethoxysilane and diphenylsilanediol. These adamantane‐based silicone resins have multifunctional groups including adamantyl group, phenyl group, and epoxy group in order to meet the various requirements for LED encapsulation. Importantly, the adamantane group in the silicone resins benefits for high refractive index and anti‐thermal properties. These APES resins were characterized by proton nuclear magnetic resonance and Fourier transform infrared spectroscopy. When APES resins were cured by methylhexahydrophthalic anhydride, they showed relatively high refractive index of 1.56, high hardness, and high thermal resistance. The encapsulated LED demonstrated high adhesion properties by red‐ink tests. These merits make adamantane‐based silicone resins promising candidates as LED encapsulation materials.     

Novel polymeric excipients for colon-targeting

Oral drug delivery to the colon is of interest for the local treatment of colonic diseases and for the systemic delivery of drugs. Our goal is to develop coating materials that are stable in gastric and small intestinal fluids and degradable in the colon by bacterial polysaccharidases. For testing colon-degradability an in vitro model was developed. A number of polysaccharide derivatives were synthesized and tested: almost completely ethylated or acetylated galactomannans, polyurethanes with galactomannan sections, crosslinked galactomannans and dextranesters of fatty acids. Generally, degradability decreased with increasing degree of substitution. Especially crosslinked galactomannan and dextranesters with a low degree of substitution or crosslinking, respectively, are promising materials. Using an industrial coating technique tablets were coated with crosslinked galactomannan and the enzymatically induced in vitro dissolution of a model drug was investigated.     

Effect of urea on the behaviour of poly(2-hydroxyethyl methacrylate)-water mixtures

The effect of urea solutions on the equilibrium swelling of lightly crosslinked poly(2-hydroxyethyl methacrylate) (PHEMA) gels and on the viscometric behaviour of PHEMA, for various concentrations of urea and temperatures, has been studied. Urea raises the degree of swelling of gels and the intrinsic viscosity of PHEMA; the temperature coefficient of both quantities is negative. A thermodynamic analysis of the swelling data shows that a change in entropy is the driving force for the increase in swelling at low temperatures, while at higher temperatures (50–80°) a negative change in enthalpy prevails, both corresponding to the transport of PHEMA from the aqueous medium into urea solutions. The entropy and enthalpy of dilution parameters derived from viscometric measurements have negative values, and their absolute values decrease with increasing urea concentration. It has also been found that the PHEMA molecules in urea solutions under the θ-conditions are much more coiled than in an organic θ-solvent. The results are interpreted in terms of the existence of inter- and intramolecular hydrophobic bonds and by the destruction of hydrophobic clusters caused by urea.     

Sorption of water in hydrophilic polymers—I Sorption isotherms in copolymers of hydroxyethyl methacrylate and hydroxyethoxyethyl methacrylate

Sorption isotherms of water vapour were determined for crosslinked poly-2-hydroxyethyl methacrylate (PHEMA), poly-2-(2′-hydroxyethoxy)ethyl methacrylate (PHEOEMA) and statistical copolymers at 35°. In the case of PHEMA the amount sorbed does not depend on the porosity of structure: sorption is influenced by the crosslinking parameters only at higher activities. The isotherm of PHEMA is S-shaped, while that of PHEOEMA, is convex; at lower activities, the sorption in mol/mol is higher in PHEMA than in PHEOEMA, although the former has a lower content of polar groups per monomer unit. It seems that the differences between isotherms could be explained by the fact (in principle identical with Kargin's hypothesis) that PHEMA is in the glassy state at the temperature of measurement, while the state of PHEOEMA is viscoelastic. The sorption data were used to calculate the parameters of the B.E.T. equation modified by Anderson; the concentrations of the sorption sites thus determined do not oppose the view that strongly bound water molecules are sorbed between two hydroxyl groups. The dependence of the Flory-Huggins interaction parameter χ on the volume fraction of the polymer exhibits a marked change of slope at a concentration roughly corresponding to the water content needed to transform the polymer from the glassy into the viscoelastic state at 35°. The Zimm clustering function indicates, at a higher water content, a considerable tende`ncy towards clustering; however, for samples in the glassy state and at low amounts sorbed, this function assumes negative values, suggesting mutual isolation of the molecules of the sorbate.     

Performance of methylphenyl hydrogen-containing silicone oils for LED encapsulation

Three-dimensional light-emitting diodes (LEDs) are the preferred light source for bulb lamps due to their 360° illumination. Addition curing silicone resins have usually been used to encapsulate LEDs. LED-filament encapsulation needs silicone resins having high thermal performance and thixotropy. Herein, a low refractive index and highly anti-thermal aging silicone oil was synthesized by hydrolysis and co-condensation method, and used to prepare an encapsulation material for high-power LED-filament. The cured silicone materials were characterized by thermogravimetric analysis (TGA) and thermal aging test under 180°C and 250°C. The results demonstrated that the thermal stability of the cured silicone resins with short-chain phenyl silicone as a crosslinker was higher than that with long-chain methyl silicone oil crosslinker. Owing to the excellent thermal stability, appropriate hardness, high transparency and photoelectric efficiency, this LED encapsulation material is a promising candidate for high-power LED package.     

Sub-micron tailoring of bi-soft segment asymmetric polyurethane membrane surfaces with enhanced hemocompatibility properties

Enhancement of membrane hemocompatibility is achieved through the control of the surface morphology. Bi-soft segment integrally skinned poly(ester urethane urea) (PEUU) membranes containing polycaprolactone (PCL) as a second soft segment are synthesized with PCL-diol ranging from 0% to 15% (w/w). Scanning electron microscopy and atomic force microscopy characterized membrane asymmetry and sub-micron roughnesses, R(a), of top dense surfaces as major assets to the development of platelet/membrane surface interactions. Here we show that the top dense surfaces of asymmetric PEUU membranes can be tailored with different morphologies when the ratio of the two soft segments PPO/PCL varies. A strong correlation between the top surface roughnesses, R(a) and platelet deposition is identified. The membrane with 15% (w/w) of PCL-diol, PEUU 85, shows the smoothest top dense layer with a R(a) as low as 1 nm which is 5 times below the characteristic value of the PEUU membrane with a single soft segment. The PEUU 85 asymmetric membrane displayed minimal platelet deposition and inhibition of extreme stages of platelet activation.     

Distribution model for the intact urokinase and urokinases modified by soluble macromolecules in rat and mouse bodies

The activity of intact urokinase (UK) and urokinases modified by soluble macromolecules (dextran and dextran sulfate sodium) in a mouse body was traced after injection of the 125I-labelled enzymes. The residual fraction of the enzyme in blood can be correlated with the time (t) as follows; Xb = Ae-at + Be-bt + Ce-ct Since a greater than b greater than c, the residual fraction of the enzyme in blood chiefly depends on the magnitude of parameter C. The constant C for modified urokinase was larger than that for urokinase, showing the relative residual in blood was increased by modification of the enzyme. The apparent utilization in 50 min was 13.8% for intact UK, 28.1% for the dextran-UK and 25.2% for the sulfate dextran-UK. Therefore, the apparent utilization of UK in blood was approximately doubled by the modification. Since the half-lives of UK and modified UK in kidney and liver were not long, there were no unacceptable accumulation of the enzymes.     

多嵌段聚醚氨酯脲为基质的新型高分子固态离子导体

本文合成了一系列聚乙二醇型多嵌段聚醚氨酯脲，而且用这类聚醚氨酯甩与高氯酸锂制得了一种新型的高分子固态离子导体复合物。在室温和50℃之间，其电导率比聚环氧乙烷为基质的固体电解质的高一到二个数量级，它还具有优良的综合性能。因此，对于室温薄膜蓄电池来说，这种新型的固体电解质是一类良好的候选材料。     

Mechanical properties of composite heterogeneous gels

Composites with a matrix of poly(2-hydroxyethyl methacrylate) (PHEMA) and 10% by volume of various crosslinked PHEMA polymer fillers (prepared by copolymerization with 0.1, 0.4, 1.0, and 20.0% by weight of ethylenedimethacrylate) of particle size about 1 μm were prepared. Some polymer matrixes were prepared from soluble branched PHEMA (Hydron S), and others by copolymerization, in the presence of the filler with 0.4 and 1.0% of ethylenedimethacrylate as a crosslinking agent. In the case of the uncrosslinked matrix, a linear polymer–crosslinked polymer system, resulted; in the case of the crosslinked matrix, a composite heterogeneous network was formed (in the latter case, the particles of the filler were swollen with monomer during the crosslinking polymerization). Stress–strain, equilibrium, and ultimate characteristics were measured at 3, 10, 25, 40, 60, and 80°C on samples swollen to equilibrium in water (T_g ≈ ?50°C) and at 80, 110, and 140°C on dry samples (T_g ≈ 100°C). Depending on experimental conditions, above all on the distance from the main transition region and on whether the polymer is dry or swollen, it was found that the measured hydrophilic composite systems behaves as a filled system (with the polymer filler acting mostly as solid particles, irrespective of the crosslink density) or as a system with crosslink density fluctuations (where both networks, the matrix and the filler, contribute roughly additively to the properties of the system), or finally as defect heterogeneous systems (where the properties depend primarily on the character of the polymer–filler interface).     

New photo‐induced thiol‐ene crosslinked films based on linear methacrylate copolymer polythiols

Thiol‐ene radical addition by photolysis is a highly efficient click reaction of sufhydryl groups with reactive enes that has been extensively explored as a promising means to construct multifunctional materials. Here, photo‐induced thiol‐ene crosslinked films composed of linear methacrylate copolymer polythiols (MCPsh) are reported. Well‐defined MCPsh copolymers were prepared by thiol‐responsive cleavage of pendant disulfide linkages positioned in the corresponding methacrylate copolymers with narrow molecular weight distribution which were synthesized by a controlled radical polymerization method. With a commercially available multifunctional acrylate as a model ene, photo‐induced thiol‐ene radical polyaddition of these polythiols is competitive to free‐radical homopolymerization of acrylates, yielding crosslinked films exhibiting rapid cure, uniform network, and enhanced mechanical properties; these properties are required for high performance coating materials. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2860–2868.     

Composites of poly (dimethylsiloxane) and spherically shaped poly (2‐hydroxyethylmethacrylate) particles for biomedical use

Silicone rubbers have shown considerable promise in the biomedical field, but their hydrophobicity leads to serious problems in long‐term implants. In our study, composites of poly (dimethylsiloxane) (PDMS) and spherically shaped poly (2‐hydroxyethylmethacrylate) (PHEMA) microparticles were prepared. Unlike previous silicone hydrogel composites, suspension polymerization was carried out in an aqueous medium to prepare PHEMA particles directly, which avoided the removal of organic phase and give hydrogel particles with high purity. Very fine PHEMA particles with uniform geometry and small size were obtained through various influencing factors during their formation. Through the introduction of PHEMA particles, PDMS matrix was endowed with hydrophilicity to a certain extent. With an increase in hydrogel content, higher swelling ability and surface wettability of the composites were observed. We have also demonstrated that smaller sized particles are more favorable for hydrophilicity improvement. The results of improved swelling ability, surface wettability, and low affinity to lipid show that this composite material is suitable for biomedical use. Copyright © 2009 John Wiley & Sons, Ltd.     

Extracting uncrosslinked material from low modulus sylgard 184 and the effect on mechanical properties

Commercial silicone elastomers are commonly used in soft materials research due to their easily tunable mechanical properties. However, conventional polydimethylsiloxane (PDMS) elastomers with moduli below ∼100 kPa contain uncrosslinked free molecules, which play a significant role in their behavior. To utilize these materials, it is important to quantify what role these free molecules play in the mechanical response before and after their removal. We present a simple and inexpensive extraction method that enables the removal of free molecules from a lightly crosslinked sheet of Sylgard 184, a commercially available PDMS elastomer. The materials can contain a majority of free molecules yet maintain a thin and flat geometry without fractures after extraction. Subsequently, we compare the modulus, maximum stretchability, and hysteresis behavior with mixing ratios ranging from 60:1 to 30:1, before and after extraction. We show that the modulus, maximum stretchability, and dissipation increase upon extraction. Moreover, our approach offers a route to prepare crosslinked silicone elastomers with a modulus as low as ∼20 kPa without free molecules from a commercially available kit. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 343–351     

Anticoagulant activity of immobilized thrombomodulin

Bovine lung thrombomodulin was partially purified, and immobilized on agarose gel (Sepharose 4B). Immobilized thrombomodulin inhibited the procoagulant activity of thrombin, and enhanced the thrombin-catalyzed protein C activation. The plasma recalcification time test showed that immobilized thrombomodulin prolonged plasma clotting time. It is suggested that the immobilization of thrombomodulin will provide an antithrombogenic biomaterial able to convert thrombin from a procoagulant to an anticoagulant enzyme.     

Hydrolytically stable thermoplastic and thermosetting poly(arylene phosphine oxide) material systems

Several thermoplastic and thermosetting polymeric materials containing the phenyl phosphine oxide group were prepared and characterized by physical methods. High molecular weight poly(arylene ether)s and polyimides containing the hydrolytically stable bulky phosphine oxide unit were synthesized and found to be soluble materials with moderately high glass transition temperatures. The phenyl phosphine oxide moiety was further incorporated into epoxy and bismaleimide type crosslinked systems. Phosphorus promoted char formation in air was displayed by both the linear and crosslinked macromolecules, leading to improved self-extinguishability relative to the non-phosphorus containing analogous polymeric systems.     

Enhanced Bone Defect Repair by Polymeric Substitute Fillers of MultiArm Polyethylene Glycol‐Crosslinked Hyaluronic Acid Hydrogels

Bone regeneration is still one of the greatest challenges for the treatment of bone defects since no current clinical approach has been proven effective. To develop an alternative biodegradable bone graft material, multiarm polyethylene glycol (PEG) crosslinked hyaluronic acid (HA) hydrogels are synthesized and applied to promote osteogenesis of mesenchymal stem cells (MSCs) with the ultimate goal for bone defect repair. The multiarm PEG‐HA hydrogels provide a significant improvement of alkaline phosphatase (ALP) activity and calcium mineralization of the in vitro encapsulated MSCs under osteogenic condition after 3, 7, and 28 days. In addition, the multiarm PEG‐HA hydrogels also facilitate healing of the cranial bone defects more effectively in a Sprague Dawley rat model after 10 weeks of implantation based on histological evaluations and microcomputed tomography analysis. These promising results set the stage for the development of innovative biodegradable hydrogels to provide a more effective and versatile treatment option for bone regeneration.     

Encapsulation of nanomaterials using an intermediary layer cross‐linkable ABC triblock copolymer

For the preparation of core‐shell nanoparticles containing functional nanomaterials, a photo‐cross‐linkable amphiphilic ABC triblock copolymer, poly(ethylene glycol)‐b‐poly(2‐cinnamoyloxyethyl methacrylate)‐b‐poly(methyl methacrylate) (PEG‐PCEMA‐PMMA), was synthesized. This triblock copolymer was then used to encapsulate Au nanoparticles or pyrene. The triblock copolymer of PEG‐b‐poly(2‐hydroxyethyl methacrylate)‐b‐PMMA (PEG‐PHEMA‐PMMA) (M_n = 15,800 g/mol, M_w/M_n = 1.58) was first synthesized by activators generated by electron transfer atom transfer radical polymerization. Its middle block was then functionalized with cinnamoyl chloride. The degrees of polymerization of the PEG, PHEMA, and PMMA blocks were 45, 13, and 98, respectively. PMMA‐tethered Au nanoparticles (with an average diameter of 3.0 nm) or pyrene was successfully encapsulated within the PEG‐PCEMA‐PMMA micelles. The intermediary layers of the micelles were then cross‐linked by UV irradiation. The spherical structures of the PEG‐PCEMA‐PMMA micelles containing Au nanoparticles or pyrene were not changed by the photo‐cross‐linking process and they showed excellent colloidal stability. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4963–4970, 2009     

Smart nanocontainers as depot media for feedback active coatings

Among the grand challenges at present are ways to develop systems with low consumption of raw materials and with little load on the environment. In view of this it is of utmost importance to avoid or to delay processes causing material destruction. This is especially urgent, since many protective substances have associated health hazards, and new routes to improve the situation are a main concern of this contribution. Nanocapsules (nanocontainers) with controlled release properties of the shell can be used to fabricate a new family of active coatings, with quick response to changes of the coating environment or coating integrity. The release of active materials encapsulated into nanocapsules is triggered by various external and internal factors, thus preventing spontaneous leakage of the active component. The coating can have several active functionalities when several types of nanocapsules loaded with corresponding active agent are incorporated simultaneously into a coating matrix. We highlight recent achievements in development and application of filled responsive containers in biomedical and self-healing protective coatings.     

Heterogeneity of glass transition dynamics in polyurethane‐poly(2‐hydroxyethyl methacrylate) semi‐interpenetrating polymer networks

The peculiarities of segmental dynamics over the temperature range of ?140 to 180 °C were studied in polyurethane‐poly(2‐hydroxyethyl methacrylate) semi‐interpenetrating polymer networks (PU‐PHEMA semi‐IPNs) with two‐phase, nanoheterogeneous structure. The networks were synthesized by the sequential method when the PU network was obtained from poly(oxypropylene glycol) (PPG) and adduct of trimethylolpropane (TMP) and toluylene diisocyanate (TDI), and then swollen with 2‐hydroxyethyl methacrylate monomer with its subsequent photopolymerization. PHEMA content in the semi‐IPNs varied from 10 to 57 wt %. Laser‐interferometric creep rate spectroscopy (CRS), supplemented with differential scanning calorimetry (DSC), was used for discrete dynamic analysis of these IPNs. The effects of anomalous, large broadening of the PHEMA glass transition to higher temperatures in comparison with that of neat PHEMA, despite much lower T_g of the PU constituent, and the pronounced heterogeneity of glass transition dynamics were found in these networks. Up to 3 or 4 overlapping creep rate peaks, characterizing different segmental dynamics modes, have been registered within both PU and PHEMA glass transitions in these semi‐IPNs. On the whole, the united semi‐IPN glass transition ranged virtually from ?60 to 160 °C. As proved by IR spectra, some hybridization of the semi‐IPN constituents took place, and therefore the effects observed could be properly interpreted in the framework of the notion of “constrained dynamics.” The peculiar segmental dynamics in the semi‐IPNs studied may help in developing advanced biomedical, damping, and membrane materials based thereon. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 963–975, 2007     

新型复合介孔材料HPMo/SBA-15的合成与表征

合成了一种新型复合介孔材料HPMo/SBA-15, 通过XRD, TEM, UV-Vis和IR等方法表征证明HPMo均匀且稳定地包藏到介孔材料SBA-15的由SiO2网络组成的孔壁中. 催化实验结果表明, 该材料在大分子催化裂化反应中具有很高的活性, 在大分子催化氧化反应中连续循环使用未发现活性组分流失, 显示了其在大分子催化和均相催化反应多相化中具有很好的应用前景.     

In situ formation of new crosslinking agents from acrylate derivatives and bisepoxides

The synthesis of several newly available diacrylate crosslinking agents derived from hydroxy functional acrylates and bisepoxides is described. These crosslinking agents are synthesized via the acid catalyzed addition of hydroxyl-containing acrylate monomers to bisepoxides derived from bisphenol-A and its hexafluoropropyl analog. These materials are generated in an excess of the acrylate monomer and the reaction mixtures are then converted directly to highly crosslinked materials. The alcohol functional monomers include hydroxyethyl methacrylate (HEMA) and the butyl and ethyl esters of (α-hydroxymethyl)acrylic acid. The latter are especially interesting for several reasons. First, they are readily available through the addition of the corresponding acrylate to formaldehyde. Second, these monomers react with the bisepoxides to give all-ether-linked connecting groups, in conrast to HEMA which yields a molecule with both ether and ester linkages between the two acrylate units. Third, the monomers are very different in solubility from HEMA and the polymers display very different chemical and physical properties. For example, while the crosslinked HEMA polymers are swellable in water, those of the (α-hydroxymethyl)acrylates are insoluble in water but swellable in organic solvents such as chloroform. All monomers, crosslinking agents, and crosslinked polymers were characterized by FT-IR, solution or solid state ¹³C-NMR spectroscopy, and thermal analysis.