Morphology and mechanical properties of poly(dimethyl siloxane-b-styrene-b-dimethyl siloxane) block copolymers

The films of poly(dimethyl siloxane-b-styrene-b-dimethyl siloxane) block copolymers cast from different solvents showed significant changes in both the phase morphology and the tensile behaviour. Methyl ethyl ketone and tetrahydrofuran gave hard films and appear to have a continuous polystyrene phase. Conversely cyclohexane, a good solvent for polydimethyl siloxane segment gave softer more elastic films. Intrinsic viscosity data of block copolymers of varying siloxane content showed highest value in toluene and least in cyclohexane which is a theta solvent for polystyrene segment. The tensile properties are also influenced by thermal ageing of films at 100 and 150°C.     

Styrene polymerization with a macroinitiator having siloxane units

Block copolymers containing segments of poly(dimethylsiloxane) (PDMS) and polystyrene were synthesized. Dihydroxy terminated PDMS M_n 2500 g/mol, was reacted with an ali-phatic diisocyanate (isophorone diisocyanate) and an aliphatic hydroperxide (t-butyl hy-droperoxide). The resulting polymeric peroxycarbamate having siloxane units (a new mac-roinitiator) was used as free radical initiator for vinyl polymerization of styrene. Formation of block copolymers was illustrated by several characterization methods such as chemical and spectroscopic analysis, fractionation, and GPC. Mechanical and thermal characterization of the copolymers were made by stress–strain tests and DSC. The surface properties and the morphology of the block copolymers were investigated by contact angle measurements and SEM. © 1996 John Wiley & Sons, Inc.     

Microphase separation in amorphous poly(imide siloxane) segmented copolymers

A series of amorphous poly(imide siloxane) (PIS) segmented copolymers with various segmental lengths and contents of poly(dimethyl siloxane) (PDMS) were synthesized by condensation polymerization. Extraction was utilized to obtain highly pure PISs for a study of phase separation. The PISs self-assemble from dilute solutions that are initially rod-like structures and then rapidly transform to vesicles. Moreover, the vesicles change to solid spheres as the PDMS content increases. A variety of morphologies of the PIS films, including unilamellar vesicle, multilamellar vesicle, sea-island and others, are found as a function of the content and the segmental length of PDMS. Small angle X-ray scattering demonstrates the coexistence of large-scale phase separations and nano-scale phase separations of approximately 20 nm. The DSC results reveal that the phase separation is induced and dominated by the aggregation of PDMS segments. Furthermore, the surfaces of the hard phases in the PDMS-900 PISs are found to be fractal.     

Preparation of poly(IPDI‐PTMO‐siloxanes) and influence of siloxane structure on reactivity and mechanical properties

Siloxane‐modified polyurethanes were prepared through isophorone diisocyanates (IPDI), poly(tetramethylene oxide) (PTMO), and siloxanes. IPDI served as the hard segment in the structure. Both PTMO and siloxanes were diols and served as the soft segments. In addition, different chemical structures of siloxanes were used, in which siloxane chains would remain in the main chain of polyurethanes (PU) or become the side chain of PU. First, the reactivities of PTMO and siloxanes to react with IPDI in bulk system were studied through DSC, in which the reaction heat was related to their reactivities. Copolymerization of IPDI, PTMO, and siloxanes in bulk were also studied. The results showed that hydrophobicity and steric hindrance of siloxane diols led to their low reactivities. Next, a series of siloxane‐modified PU in toluene solvent were synthesized, and the conversion of NCO groups was determined by the method of chemical titration. In the synthesis of PU copolymers in a solution polymerization, because of low reactivity of siloxanes, a two‐step procedure was adopted. The siloxane diol was first reacted with IPDI in toluene to form NCO‐terminated prepolymer. Then PTMO was added to form final PUcopolymers. The addition of side‐chain siloxanes resulted in PU copolymers with higher molecular weight than main‐chain siloxanes. Both main‐chain and side‐chain siloxanes increased the elongation at break and tensile strength of final PU copolymers. The microphase‐separation of siloxane segments was observed by SEM, which was the main cause for the improved mechanical properties. POLYM. ENG. SCI., 47:625–632, 2007. © 2007 Society of Plastics Engineers.     

Synthesis and characterization of multiblock copolymers containing poly(dimethyl siloxane) blocks

Multiblock copolymers of polystyrene and poly(dimethyl siloxane) were obtained by a hydrosilylation reaction between a,w dihydrogeno poly(dimethyl siloxane) and a,w-di(vinyl silane) polystyrene. Under well chosen experimental conditions the polycondensation is free of site reactions and the macromolecules formed are linear with up to 10 blocks, which corresponds to reaction of 90% of the functions initially present. The block copolymers obtained have been characterized by g.p.c. viscosimetry and light scattering.     

Non-aqueous polymer dispersions: dimensions of adsorbed AB block copolymers of polystyrene and poly(dimethyl siloxane) by small-angle neutron scattering

Poly(methyl methacrylate) and polystyrene particles stabilized in n-heptane, Freon 113 (1,1,2-trichloro-1,2,2-trifluoroethane) and silicone fluid by AB block copolymers of polystyrene and poly(dimethyl siloxane) have been studied using small angle neutron scattering. Particle sizes calculated from the scattering intensity are in reasonable agreement with particle diameters estimated from electron micrographs. The intensity of scattering from poly(methyl methacrylate) particles stabilized with copolymers containing A blocks prepared from perdeuterostyrene was much higher than from polystyrene particles stabilized with the same block copolymers. It is proposed that the polystyrene blocks are molecularly dispersed in polystyrene particles and cluster into domains in poly(methyl methacrylate) particles. Scattering arising from the poly(dimethyl siloxane) blocks has been detected but could not be simply interpreted.     

Low earth orbit resistant siloxane copolymers

Two classes of siloxane copolymers were evaluated for their resistance to the low earth orbit (LEO) environment. Poly(imide–siloxane) (PISX) copolymers were used as the resin for PISX–carbon fiber composites. These composites were exposed to the LEO environment, for 50 h, as part of the “Effect of Oxygen Interaction with Materials” (EOIM-III) experiment aboard the space shuttle STS-46. XPS analysis showed primarily silicon oxides on the LEO-exposed surfaces and evidence of a thermally accelerated oxidation. The results of simulated LEO exposure of the PISX composites show that they are one to two orders of magnitude more resistant than are homopolyimide-based composites. Furthermore, we found, surprisingly, that these materials erode slower when far-UV radiation is combined with the atomic oxygen. XPS analysis of PISX exposed only to far-UV allowed a partial mechanism to be proposed for the effect of far-UV radiation on the PISX copolymers. Polyhedral oligosilsequioxane (POSS)–siloxane copolymers were evaluated in a simulated LEO environment and results indicate that the POSS–siloxane copolymers are even more resistant to the simulated LEO environment than are the PISX copolymers; POSS–siloxanes actually gained weight during the exposure and healed the microcracks present. © 1996 John Wiley Sons, Inc.     

Synthesis and properties of polyurethane modified with aminoethylaminopropyl poly(dimethyl siloxane)

A series of polyurethanes with different siloxane contents were synthesized, which were based on 4,4′‐methylene diphenyl diisocyanate (MDI), poly(tetramethylene oxide) (PTMO), aminoethylaminopropyl poly(dimethyl siloxane) (AEAPS), and butanediol (BD). The chemical compositions, structures, and bulk and surface properties were investigated using an infrared surface quantitative analysis technique (FTIR‐ATR), surface contact angle, electron spectroscopy for chemical analysis (ESCA), stress–strain analysis, and dynamic mechanical thermal analysis (DMTA). It was shown that siloxane concentration on the surface region of the elastormers was higher than that in the bulk for a resulting surface enrichment of the siloxane, and the tensile properties of these elastomers were not changed significantly with the AEAPS modification. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2552–2558, 1999     

The effect of the mass ratio of hard and soft segments on some properties of thermoplastic poly(ester‐siloxane)s

A series of thermoplastic elastomers based on soft polydimethylsiloxane (PDMS) and hard poly(butylene terephthalate) (PBT) segments was synthesized using a two‐step transesterification reaction in the melt. The molar mass of the soft PDMS component was constant (M?_nPDMS = 1056 g mol^?1) while the starting reaction mixture compositions were varied to obtained copolymers with a mass ratio of hard to soft segments in the range from 70/30 to 40/60. The structure and composition of the copolymers was verified by ¹H NMR spectroscopy. It appeared that there was a pronounced molar mass maximum when the PBT content of the copolymers was approximately 60 mass%, whereas all samples were considerably inhomogeneous with respect to the distribution of the lengths of the hard segments. Differential scanning calorimetry (DSC) thermograms showed that the melting and crystallization temperature increased with increasing PBT content, as did the total degree of crystallinity, which was confirmed by wide‐angle X‐ray scattering (WAXS) analysis. Thermogravimetric analysis (TGA) performed in nitrogen gave subtle differences for samples of different composition, including that of the PBT homopolymer, whereas in oxygen these differences were more pronounced in the way the thermo‐oxidative stability of the obtained copolymers decreased with decreasing PBT content. Finally, it was shown that the hardness depended directly on the PBT content, ie the higher the PBT content, the greater the hardness of the corresponding copolymer. Copyright © 2004 Society of Chemical Industry     

Mechanical properties of polysiloxanes: 1. Poly(tetramethyl-p-silphenylene siloxane) homopolymer and tetramethyl-p-silphenylene siloxane/dimethyl siloxane block copolymers

The mechanical behaviour of poly(tetramethyl-p-silphenylene siloxane) [poly(TMPS)] homopolymer and random block copolymers of tetramethyl-p-silphenylene siloxane-dimethyl siloxane [poly(TMPS-DMS)] of mean DMS block of 12 monomer units have been investigated over a wide range of composition and temperature using a Rheovibron viscoelastometer. The compositions ranged from TMPS/DMS wt % ratio of $\text{100}\text{0}$ to $\text{30}\text{70}$. The temperature intervals spanned from just above ?120°C to the point where melting became evident as dictated by the molecular architecture of each system. Two amorphous relaxation transitions, corresponding to DMS and TMPS phases, were found for copolymers with high TMPS content (?80 wt %). At lower TMPS compositions (?50 wt %) these transitions merge together. All dynamic transitions are a function of composition and crystallinity. The ‘hard’ TMPS phase provides crosslinks and acts as filler for the rubbery amorphous phase. The percentage elongation under tensile loading increases with the DMS amorphous content, which parallels an increase in clarity and decrease in density and crystallinity. A morphological model which depends on composition is proposed for these polysiloxanes. The model advanced is consistent with other physical evidence derived from other techniques. Changes in mechanical behaviour parallel changes in specimen morphology.     

Synthesis and properties of novel benzocyclobutene‐functionalized siloxane thermosets

Two kinds of novel benzocyclobutene (BCB) functionalized monomers were synthesized through imidization of siloxane‐containing dianhydride with 4‐aminobenzocyclobutene. The BCB monomers obtained exhibited good solubility in various organic solvents. They were converted into crosslinked polymer via ring opening and the following Diels–Alder reaction at proper temperature. The curing kinetics were studied by non‐isothermal differential scanning calorimetry. The BCB polymers showed good thermal stability, excellent dielectric properties, low water absorption and good planarization. Moreover, the thermal and mechanical properties of the BCB resins could be adjusted by the length of the siloxane unit. The BCB resins with a shorter siloxane chain exhibited higher glass transition temperature, higher modulus and lower coefficient of thermal expansion than BCB resins with longer chains. © 2013 Society of Chemical Industry     

Synthesis,characterization, and comparison of properties of novel fluorinated poly(imide siloxane) copolymers

Four new poly(imide siloxane) copolymers were prepared by a one‐pot solution imidization method at a reaction temperature of 180°C in ortho‐dichlorobenzene as a solvent. The polymers were made through the reaction of o‐diphthaleic anhydride with four different diamines—4,4′‐bis(p‐aminophenoxy‐3,3″‐trifluoromethyl) terphenyl, 4,4′‐bis(3″‐trifluoromethyl‐p‐aminobiphenyl ether)biphenyl, 2,6‐bis(3′‐trifluoromethyl‐p‐aminobiphenyl ether)pyridine, and 2,5‐bis(3′‐trifluoromethyl‐p‐aminobiphenylether)thiopene—and aminopropyl‐terminated poly dimethylsiloxane as a comonomer. The polymers were named 1a , 1b , 1c , and 1d , respectively. The synthesized polymers showed good solubility in different organic solvents. The resulting polymers were well characterized with gel permeation chromatography, IR, and NMR techniques. ¹H‐NMR indicated that the siloxane loading was about 36%, although 40 wt % was attempted. ²⁹Si‐NMR confirmed that the low siloxane incorporation was due to a disproportionation reaction of the siloxane chain that resulted in a lowering of the siloxane block length. The films of these polymers showed low water absorption of 0.02% and a low dielectric constant of 2.38 at 1 MHz. These polyimides showed good thermal stability with decomposition temperatures (5% weight loss) up to 460°C in nitrogen. Transparent, thin films of these poly(imide siloxane)s exhibited tensile strengths up to 30 MPa and elongations at break up to 103%, which depended on the structure of the repeating unit. The rheological properties showed ease of processability for these polymers with no change in the melt viscosity with the temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanism study on surface activation of surfactant‐modified polyvinyl siloxane impression materials

This study examined the mechanism on the surface activation of hydrophilic polyvinyl siloxane impression materials incorporated with nonionic surfactants. Hydrophilic polyvinyl siloxane impression materials were prepared with a polydimethylsiloxane composition and nonionic surfactants. The surfactants used were nonylphenoxy poly(ethyleneoxy) ethanol homologs of varying ethyleneoxy chain length. These homologs were designated NP4, NP6, and NP10 according to the mole number of ethyleneoxy group (hydrophilic group) of 4, 6, and 10, respectively. The incorporation of a nonionic surfactant into polyvinyl siloxanes enhanced their hydrophilicity and consequently led to the significant reduction in the contact angles. The higher the concentration of surfactant that was incorporated, the lower the contact angles that were observed. The contact angle was lowest when NP4 was incorporated, even though NP4 is less hydrophilic than NP6 and NP10, which implies that the exposed surfactant concentration on the surface was highest when NP4 was used. Relatively lower surface energy of NP4 among three surfactants would induce spatial distribution of NP4 on the hydrophobic surface of polyvinyl siloxane and consequently resulted in higher surfactant concentration on the surface of the silicone impression material. The surfactant dispersion size also seemed to be relevant for the surface activation in these surfactant‐modified silicone impression materials. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2395–2401, 2004     

Thermogravimetric analysis of blends of low‐density polyethylene and poly(dimethyl siloxane) rubber: The effects of compatibilizers

The thermal stability of vulcanizates of low‐density polyethylene (LDPE), poly(dimethyl siloxane) (PDMS) rubber, and their blends was studied by nonisothermal thermogravimetry. Four ethylene copolymers [ethylene methyl acrylate (EMA), ethylene vinyl acetate, ethylene acrylic acid, and a zinc‐salt‐based ionomer (Lotek 4200)] were used as compatibilizers for the blend systems. The thermograms and derivatograms of the blends showed that thermal degradation took place in two stages, whereas those for the base polymers showed single‐stage degradation. Kinetic studies of the blends and pure components showed that the degradation followed first‐order reaction kinetics. The activation energy at 10% degradation was determined with the Freeman–Carroll method and was at a maximum (42.34 kcal/mol) for the 25:75 LDPE/PDMS rubber blend. The half‐life at 200°C was evaluated by the Flynn–Wall method and was at a maximum (812.5 days) for the same blend. Out of four compatibilizers, EMA showed the maximum activation energy (34.25 kcal/mol) for degradation and a maximum half‐life (695.3 days), indicating that EMA was the best compatibilizer for the blend system. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 635–642, 2003     

Compounding of poly(dimethyl siloxane) to reduce tack in natural rubber

Tack in natural rubber latex was reduced by compounding poly(dimethyl siloxane) (PDMS) emulsion in concentrated latex. Sheet and dipped film surfaces were examined with Fourier transform infrared spectroscopy using attenuated total reflection (FTIR–ATR) and by contact angle measurements. Autohesive tack and tensile properties were also determined. For both sheet and dipped film, FTIR–ATR showed that the PDMS concentration was higher at the glass surface than at the air surface. The contact angle of ethylene glycol on the rubber decreased with increasing PDMS content. Autohesive tack for sheet and dipped film also decreased with increasing PDMS amount; however, annealing for 1 week at 70°C in air did cause tack to rise in the sheets. The rubber surface could be made nonadhesive by addition of sufficient PDMS. PDMS caused a decrease in tensile strength for the sheet, especially after annealing; however, PDMS did not cause a substantial decrease in percentage elongation for the sheets, except at relatively high PDMS contents. The tensile strength and percentage elongation for dipped film was not affected by PDMS over the much more limited PDMS concentration range studied. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 519–526, 2001     

Preparation and characterization of crosslinked polyurethane‐block‐poly(trifluoropropylmethyl)siloxane elastomers with potential biomedical applications

A series of crosslinked polyurethane‐block‐poly(trifluoropropylmethyl)siloxane elastomers were prepared via two steps. First, poly(trifluoropropylmethyl)siloxane polyurethane (FSPU) prepolymers were synthesized with α,ω‐bis(3‐aminopropyldiethoxylsilane) poly(trifluoropropylmethyl)siloxane (APFS) and toluenediisocyanate (TDI) and then capped with butanediol to generate the macromolecular FSPU diol extender. Second, polyurethane prepolymers synthesized from poly(tetramethylene oxide) and TDI were reacted with FSPU diol extenders with different ratios. The copolymers formed films through moisture curing and were characterized by Fourier transform infrared spectroscopy, DSC, dynamic mechanical analysis, TGA, mechanical testing etc. It is found that the equivalent ratio of reactants gives rise to a high molecular weight of copolymers and that low molecular weight APFS in the copolymers can form a certain number of silicon–oxygen crosslinks resulting from silicon alkoxy to produce higher tensile strength elastomers. The material thus has higher thermal stability and a more stable surface performance. The copolymers are then good candidates for biomedical applications.© 2013 Society of Chemical Industry     

Polydimethylsiloxane-modified chitosan I. Synthesis and structural characterisation of graft and crosslinked copolymers

Graft and crosslinked polydimethylsiloxane (PDMS)-chitosan copolymers were prepared through the reaction between mono and difunctional glycidoxypropyl-terminated PDMSs and chitosan. The transformation of amino groups of chitosan through the reaction with epoxy groups was confirmed by FT-IR and ¹³C cross-polarization (CP) magic-angle spinning (MAS)-NMR analysis. Chitosan-based materials modified with about 40% and 60% hydrophobic polydimethylsiloxane were obtained, respectively. As proved by wide angle X-ray analysis, the crystallinity of chitosan was strongly decreased through the incorporation of PDMS sequences. However, both graft and crosslinked copolymers still present a partial crystalline structure. Their X-ray patterns are not only different as compared to chitosan but also as compared to each other. For the graft copolymer, three diffraction peaks were observed at 2θ = 8.4°, 11.2° and 21.2°, indicating the formation of a new partially crystalline phase and the modification of the interplanar distances for the phases similar to chitosan. The crosslinked copolymer is even less crystalline, the peak around 2θ = 20° being strongly decreased. Different thermal behaviour of siloxane modified chitosan was registered for graft and crosslinked copolymers; the graft sample is less stable than chitosan, while the crosslinked copolymer showed an intermediate stability between chitosan and polydimethylsiloxane precursors.     

Si-C型聚醚改性硅油的制备

研究了以烯丙基聚乙二醇甲基醚和低含氢硅油为原料,甲苯为溶剂,自制的催化剂,制备Si-C型聚醚改性聚硅氧烷,较适宜的合成条件为:选择相对分子量为1 000的聚醚,n(硅氢键)∶n(聚醚)=1∶1.2,反应温度90℃,催化剂用量为30×10-6,甲苯用量为总反应体系质量的25%。合成的聚醚改性硅油透明,性能优越,使用范围较广。     

Block copolymers derived from azobiscyanopentanoic acid. XI. Properties of silicone–PMMA block copolymers prepared via polysiloxane(azobiscyanopentanamide)s

Mechanical, thermal, and surface properties of poly(dimethylsiloxane)–poly(methyl methacrylate) block copolymers (PDMS-b-PMMA) prepared by the use of polysiloxane(azobiscyanopentanamide)s were intensively investigated. The mechanical strength of block copolymers was found to decrease with an increase of siloxane contents. Dynamic mechanical analysis (DMA) of block copolymers having long siloxane chain length (SCL) and high siloxane content revealed the existence of two glass transitions attributable to microphase separation of two segments. Differential scanning calorimetry (DSC) also gave some evidence of microphase separation supporting the DMA results. It was observed that the incorporation of PDMS segments in block copolymers improved thermal stability of PMMA, as confirmed by thermogravimetric analysis. Surface analysis of the block copolymers films cast from several solutions indicated surface accumulation of PDMS segments, as revealed by water contact angle and ESCA measurements.     

Interplay of the polymer stiffness and the permeability behavior of silane and siloxane polymers

The effect of the modification of the molecular structure on the stiffness of the polymeric backbones in relation to the diffusion coefficients of typical rubbery and glassy silane and siloxane polymers at different temperatures was investigated. The inflexibility in the polymeric chains as deduced by higher values for the persistence length was shown to correspond consistently to lower values for the self-diffusion coefficients. Increasing the temperature resulted in decreasing the persistence length of the silane polymers and increasing it in the case of the siloxane polymers. This was found to be due to the fact that the bond angle about the oxygen atoms is approximately 144° and rotations about the oxygen atoms for the trans isomeric states will bring the side groups on the neighboring Si-atoms in close proximity to each other thus increasing the torsional energies of the trans isomeric states considerably. The obtained simulation results showed an excellent agreement to those determined experimentally.