Synthesis,thermal, and dynamic mechanical properties of 1,3‐bis(diphenylsilyl)‐2,2,4,4‐tetraphenylcyclodisilazane‐containing polydimethylsiloxanes

New and effective approaches to the synthesis of 1,3‐bis(diphenylsilyl)‐2,2,4,4‐tetraphenylcyclodisilazane‐containing polydimethylsiloxanes ( P1 and P2 ) were developed. P1 was obtained by polycondensation of cyclodisilazane lithium salt and chloroterminated polydimethylsiloxane. P2 was produced by hydrosilylation of vinyl‐terminated cyclodisilazane and hydrogen‐terminated polydimethylsiloxane. The polycondensation completed quickly at room temperature, while the hydrosilylation was facile and did not require cumbersome air‐sensitive operations. P1 and P2 were characterized by Fourier transform infrared, nuclear magnetic resonance, gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis (TGA), and isothermal gravimetric analysis (IGA). TGA revealed the outstanding thermal properties of P1 and P2 with 5% weight loss temperatures (T_d5) higher than 450°C. IGA proved their better thermal stability at 450°C for 800 min, compared to polydimethyldiphenylsiloxane. Dynamic mechanical analysis showed that silicone rubbers made from cyclodisilazane‐containing polydimethylsiloxanes could have a maximum tan δ value as high as 1.13 and had good prospects for damping material applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polysiloxanes containing crosslinkable diacetylene units in the main chain

The oxidative coupling of telechelic [2‐(propyn‐1)oxyethyl]oxypropyl‐terminated polydimethylsiloxanes, with the use of copper (I) chloride/TMEDA complex as the coupling catalyst, is described. The results of the studies on the influence of the reaction parameters (the catalyst concentration, the oxygen flow‐rate and the nature of the solvent) are presented. UV curing of the polymers obtained in the course of the oxidative coupling is reported Copyright © 2003 Society of Chemical Industry     

Supramolecular association of acid terminated polydimethylsiloxanes

Summary. Benzoic acid terminated polydimethylsiloxanes (PDMS) have been synthesized by hydrosilylation of allyloxybenzylbenzoate with SiH terminated precursors followed by deprotection. These oligomers have been characterized by ¹H, ¹³C and ²⁹Si NMR, by FTIR and by SEC in tetrahydrofurane. Because of the flexibility and low polarity of the siloxane backbone, they are ideally suited to study the effect of hydrogen bonding on macromolecular properties. Received: 17 July 1997/Revised: 22 July 1997/Accepted: 6 August 1997     

Functional polysiloxanes

Summary Carboxyester- and carboxyamido-terminated polydimethylsiloxanes were obtained through the reaction of cyclic anhydrides (succinic, maleic and phthalic anhydride) with hydroxypropyl- and aminoalkyl-terminated polydimethylsiloxanes, respectively. The reactivity of the starting compounds and the influence of the reaction conditions on the characteristics of the final products are discussed.Part 1: Eur. Polym. J., in press     

Tetramethylammonium 3-aminopropyl dimethylsilanolate—aminopropyl dimethylsilanolate—a new catalyst for the synthesis of high purity,high molecular weight α,ω-bis(aminopropyl) polydimethylsiloxanes

Tetramethylammonium 3-aminopropyl dimethylsilanolate, readily prepared from bis(3-aminopropyl) tetramethyldisiloxane and tetramethyl-ammonium hydroxide pentahydrate, has been found to serve as a highly effective catalyst for the ring opening polymerization of cyclic siloxanes with an end blocker such as bis(3-aminopropyl) tetramethyldisiloxane to give aminopropyl terminated linear polydimethylsiloxanes. By following a novel two stage procedure, even high molecular weight (5,000–55,000 g/mol) silicone diamines were able to be prepared in a high state of purity; chain extension reactions of these diamines with diisocyanates gave a series of high molecular weight silicone polyureas with good elastomeric properties.     

Synthesis and modification of trifunctional epoxy resin with amine terminated polydimethyl siloxanes for semiconductor encapsulation application

Epoxy resins based on the triglycidyl ether of tris(hydroxyphenyl)methane (TETM) possess a very high heat distortion temperature and superior thermal oxidative stability over other types of epoxy resins. The high performance trifunctional epoxy resin (TETM) was synthesized by the condensation of a hydroxybenzaldehyde with phenol followed by epoxidation with a halohydrin. The structure of the synthesized TETM was confirmed by infrared (IR), mass spectra (MS), and nuclear magnetic resonance (NMR) spectroscopy. Amine terminated polydimethylsiloxanes (ATPDMS) were used to reduce the stress of trifunctional epoxy resin cured with phenolic novolac resin for electronic encapsulation applications. The dispersed silicone rubbers effectively reduce the stress of cured epoxy resins by reducing the coefficient of thermal expansion (CTE) and flexural modulus, while the glass transition temperature (T_g) is depressed by only a small amount.     

Controlled drug release of silicone‐based adhesive‐containing cross‐linked siloxane powders as a reservoir

We prepared pressure‐sensitive adhesive (PSA)‐containing cross‐linked siloxane powders (CS) as a reservoir for a transdermal drug delivery system (TDDS) and evaluated their sustained drug‐release properties. PSA, as a patch‐type adhesive, was synthesized by a hydrosilylation reaction of vinyl‐terminated polysiloxanes with hydrogen‐terminated polydimethylsiloxanes. CS was also prepared via a hydrosilylation process with vinyl‐terminated polydimethylsiloxane, 1,3,5,7‐tetramethyl‐1,3,5,7‐tetravinyltetracyclosiloxane ( ), hydrogen‐terminated polydimethylsiloxane, and dimethylhydrogenmethyl oligomeric siloxane copolymer. The results of release performances using ascorbic acid as a model drug showed a cumulative linear slope over a week, indicating a constant release performance. Our data suggest that this siloxane TDDS could be useful for constant drug release over a long period. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42154.     

Synthesis and characterization of hydroxypropyl terminated polydimethylsiloxane‐polyurethane copolymers

Polyurethane (PU) block copolymers were synthesized using prepared hydroxypropyl terminated polydimethylsiloxane (HTPDMS MW 990) and polyether diols (N‐210) as soft segment with 4,4′‐diphenylmethane diisocyanate (MDI) and 1,4‐butanediol. This low molecular weight polydimethylsiloxanes (PDMS) containing hydroxypropyl end‐groups displayed better compatibility with PU than common PDMS. In this article, we illustrate its synthesis routes and confirmed the proposed molecular structures using NMR and infrared radiation (IR). We varied the contents of HTPDMS and N‐210 in soft segments (HTPDMS—N‐210: 0 : 100, 20 : 80, 40 : 60, 60 : 40, 80 : 20, and 100 : 0) to synthesize a series of PDMS‐PU copolymer. IR spectroscopy showed the assignment characteristic groups of each peak in copolymers and confirmed that the desired HTPDMS‐PU copolymers have been prepared. The different thermal, dynamic mechanical and surface properties of the copolymers were compared by thermogravimetry, DMA, contact angle and solvent resistance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Modification of cyclohexanone–formaldehyde resins with silicone tegomers

Cyclohexanone–formaldehyde resins were modified in situ with α,ω‐diamine polydimethylsiloxanes and α,ω‐dihydroxy polydimethylsiloxanes. Melting points, solubilities in organic solvents, gel permeation chromatographs, Fourier transform infrared spectra, and NMR spectra of the modified resin were determined, and the surface properties of the resins were investigated by contact angle measurements. A small amount of silicon compounds seemed to effect the physical properties of the cyclohexanone–formaldehyde resins significantly. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 97–101, 2005     

Synthesis of amphiphilic triblock copolymers for the formation of magnesium fluoride (MgF2) nanoparticles

A series of amphiphilic poly(2‐hydroxyethyl methacrylate)‐b‐polydimethylsiloxane‐b‐poly(2‐hydroxyethyl methacrylate) (pHEMA‐b‐PDMS‐b‐pHEMA) (A‐B‐A) triblock copolymers were synthesized from three different carbinol‐terminated polydimethylsiloxanes with varying molecular weight. A carbinol‐terminated polydimethylsiloxane was modified with 2‐bromoisobutyryl bromide to obtain a macroinitiator. The block copolymers were characterized by NMR, GPC, and dynamic light scattering (DLS). Reverse micelles of a copolymer were formed in mixture of benzene/methanol solution which served as nanoreactors for the synthesis of magnesium fluoride (MgF₂) nanoparticles. The MgF₂ was prepared via chemical precipitation using magnesium chloride and potassium fluoride as reactants. The MgF₂‐triblock copolymer composites were synthesized as a function of MgF₂–weight ratio (0.5, 5, and 10 wt%) in copolymer. The MgF₂ colloids were dissolved in three organic solvents: methanol, isopropanol, and tetrahydrofuran. The polymer nanoparticles were characterized by DLS, transmission electron microscopy, thermogravimetric analysis, and X‐ray diffraction (XRD) analysis. The formation of MgF₂ crystals was observed by XRD. Particle size and particle size distribution showed significant changes in different solvents. The thermal stability of MgF₂ colloids increased as the amount of nanoparticle increased in polymeric matrix. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Polydimethyldiphenylsiloxanes/silica interconnected networks: preparation and properties evaluation

A series of copolymers, polydimethyldiphenylsiloxane-α,ω-diols, differing by compositions and molecular masses has been prepared by equilibrium anionic ring-opening copolymerization of octamethylcyclotetrasiloxane with octaphenylcyclotetrasiloxane in presence of tetramethylammonium hydroxide as a catalyst. These copolymers were used as matrix for the in situ developing silica networks. The crosslinking of the copolymers concomitantly occurs by reaction between the ending silanol groups and tetraethoxysilane, thus the polydiorganosiloxane network interconnects with the silica one. The resulted materials processed as films (thickness 0.25–1.50 mm) were investigated by various techniques in order to evaluate morphology, optical properties, and thermal behavior. The results were compared with those obtained by model samples based on polydimethylsiloxanes/silica.     

New arylidene–siloxane polyethers: Liquid‐crystalline and photosensitive properties

By polycondensation reactions, starting from α, ω‐bis(chloromethyl)polydimethylsiloxanes with different molecular weights and 2,6‐bis(4‐hydroxybenzylidene)cyclohexanone, new polyethers were obtained. The structure of resulting polymers was confirmed by IR and ¹H‐NMR spectroscopy and their thermal properties and mesophase behavior were studied by TGA, DSC, and polarizing light microscopy. Depending on the length of the siloxane spacer, some of the obtained compounds exhibited thermotropic liquid‐crystalline properties. A possible smectic texture was investigated by X‐ray diffraction measurements at room temperature. A decrease of the transition temperatures values was observed as the spacer length increased. The photochemical behavior of the siloxane polyethers was studied by ultraviolet absorption spectroscopy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3093–3099, 2003     

Self‐healing supramolecular elastomers based on the multi‐hydrogen bonding of low‐molecular polydimethylsiloxanes: Synthesis and characterization

Novel self‐healing supramolecular elastomers based on polydimethylsiloxanes (SESi) were synthesized from a mixture of polydimethylsiloxanes derivers with single, di‐, or tri‐carboxylic acid groups (PDMS–COOH_x, where x = 1, 2, and 3, respectively), diethylene triamine, and urea with a two‐stage procedure. The reactions and the final products were tracked, characterized, and confirmed by Fourier transform infrared spectroscopy, ¹H‐NMR, differential scanning calorimetry, dynamic mechanical analysis, and gel permeation chromatography. Compared with a supramolecular rubber based on dimer acid (reported previously) with a similar synthesis procedure, the SESi showed a lower glass‐transition temperature of about ?113°C for the softer chain of polydimethylsiloxane and showed real rubberlike elastic behavior and self‐healing properties at room temperature or even lower temperatures. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

羟烃基聚硅氧烷的制备及亲水性能

以八甲基环四硅氧烷(D4)、四甲基环四硅氧烷(D4H)和六甲基硅氧烷(MM)为原料实施开环聚合反应,制备出不同含氢量的聚二甲基硅氧烷;含氢硅氧烷与乙酸乙烯酯进行硅氢加成反应,在硅氧烷大分子侧链上引入酯基;然后碱性条件下进行醇解反应,最后成功合成了不同羟烃基含量的聚硅氧烷.对产物的结构、乳化稳定性、乳液粒径及成膜的表面性...     

二甲基氯硅烷的合成及应用

本文介绍了二甲基氯硅烷（Ｍｅ＿２ＳｉＨＣｌ）的合成方法，由它制备Ｈ－封端聚甲基硅氧烷以及用于改性有机聚合物的活性硅油。     

Effect of the incorporation of hydroxy‐terminated liquid silicones on the cure characteristics,morphology, and release of a model protein from silicone elastomer‐covered rods

Silicone elastomer systems have previously been shown to offer potential for the sustained release of protein therapeutics. However, the general requirement for the incorporation of large amounts of release enhancing solid excipients to achieve therapeutically effective release rates from these otherwise hydrophobic polymer systems can detrimentally affect the viscosity of the precure silicone elastomer mixture and its curing characteristics. The increase in viscosity necessitates the use of higher operating pressures in manufacture, resulting in higher shear stresses that are often detrimental to the structural integrity of the incorporated protein. The addition of liquid silicones increases the initial tan δ value and the tan δ values in the early stages of curing by increasing the liquid character (G″) of the silicone elastomer system and reducing its elastic character (G′), thereby reducing the shear stress placed on the formulation during manufacture and minimizing the potential for protein degradation. However, SEM analysis has demonstrated that if the liquid character of the silicone elastomer is too high, the formulation will be unable to fill the mold during manufacture. This study demonstrates that incorporation of liquid hydroxy‐terminated polydimethylsiloxanes into addition‐cure silicone elastomer‐covered rod formulations can both effectively lower the viscosity of the precured silicone elastomer and enhance the release rate of the model therapeutic protein bovine serum albumin. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polysiloxanes With Quaternary Ammonium Salt Biocidal Functions and Their Behavior When Incorporated Into a Silicone Elastomer Network

Polysiloxanes of various structures having biocidal quaternary ammonium salt (QAS) groups pendant to the polymer chain were prepared. Their antibacterial activities were compared in aqueous solution. Selected polysiloxanes were linear polydimethylsiloxanes having 20% siloxane units substituted at silicon by 3(dimethyl-n-octylammonio)propyl chloride or 3(dimethyl-n-hexadecylammonio)propyl chloride and terminated by silanol functions at both chain ends. They were crosslinked and also incorporated by co-crosslinking into an RTV (room temperature vulcanized) silicone elastomer. Bacteriocidal activities of surfaces of the crosslinked biocidal polysiloxanes and of the elastomers having incorporated these polymers were determined by the colony count method. Thousand-fold reduction of Staphylococcus aureus in contact with the dimethyl-n-octylammonio substituted polymer was achieved in 2 min and in contact with the elastomer containing 20 wt% of this polymer in 15 min, although the density of the QAS was as low as 0.36 mmol/g. The surface structure and properties of the elastomers were studied by XPS, contact angle, AFM and model human serum protein (HSA) adsorption. Water sorption by this material was also studied. The concentration of QAS groups on the elastomer surface depended strongly on the material surroundings. No QAS was found on the surface in ultrahigh vacuum, while a strong enhancement of QAS presence on the surface was observed when it was in contact with water or water vapor. Hydrophobicity of the elastomer surface was little affected by the incorporated biocidal QAS-containing polysiloxane when the elastomer was kept in air. This material showed little ability to adsorb the HSA protein from its aqueous solution.     

有机硅改性聚氨酯合成革涂饰剂的合成及性能

用聚醚多元醇(PPG)、聚二甲基硅氧烷(PDMS)、异佛尔酮二异氰酸酯(IPD I)、1,4-丁二醇(BDO)等为主要原料,合成了有机硅改性聚氨酯溶液。通过对合成条件的考察发现,反应温度为65℃,反应4 h,采用m(丁酮)∶m(二甲苯)=1∶1作溶剂,可得到黏度适中、性能良好的产品。考察了聚二甲基硅氧烷质量分数〔w(PDMS)〕对有机硅改性聚氨酯溶液及其成膜性能的影响。结果发现,随着w(PDMS)增加,溶液的黏度降低,成膜的热稳定性提高,当w(PDMS)=10%时成膜的水接触角达到最大值102.6°。     

Syntheses of triblock polybutadiene–polydimethylsiloxane copolymers by coupling reactions

The reaction of epoxy‐telechelic polydimethylsiloxanes with polybutadienyllithium was used to prepare a series of low‐molecular‐weight polybutadiene‐block‐polydimethylsiloxane‐block‐polybutadiene copolymers. The copolymers were purified by repeated fractional precipitation/centrifugation and characterized with NMR, vapor pressure osmometry, size exclusion chromatography, and elemental analysis. The applicability of this method is discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3233–3240, 2006