Preparation and properties of poly(siloxane‐ether‐urethane)‐acrylic hybrid emulsions

Poly(siloxane‐ether‐urethane)‐acrylic (PU‐AC) hybrid emulsions were prepared by introducing different hydroxyethoxypropyl‐terminated polydimethylsiloxane (PDMS) content into the acrylic‐terminated poly(ether‐urethane) backbone and then in situ copolymerizing with methyl methacrylate and butyl acrylate via emulsion process. The effects of PDMS on the particle size and viscoelastic behavior of the hybrid emulsions were investigated. Meanwhile, the hydrogen bonding, mechanical and thermal mechanical properties, water resistance, the surface gloss, and wettability of the resultant hybrid films were also studied. The results showed that all the hybrid emulsions showed shear‐thinning behaviors, and the introduction of PDMS resulted in the formation of the hybrid emulsions with increased average particle size and decreased viscosity. The chemical bonds built between PU and AC yielded higher than 73% crosslinking fraction in all the hybrid materials, but this value decreased with increasing PDMS content because PDMS reduced the hydrogen bonding interactions and enhanced the phase separation. As a result, an increase in the PDMS content led to an increase in the elongation, water resistance, surface roughness, and water hydrophobic of the films, but the tensile strength, hardness, storage modulus, and glass transitions temperature decreased. It is suggested that introduction of PDMS can provide the hybrid materials with the improved flexibility, water resistance, and surface hydrophobicity, which has potential application value in the fouling‐release coatings, biomaterials, and surface fishing. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44927.     

Preparation and properties of fluorinated silicon two‐component polyurethane hydrophobic coatings

A polyurethane (PU) hydrophobic coating was prepared by the two‐component method, polycarbonate diol and isophorone diisocyanate becoming a two‐phase composition. The PU films with hydrophobic surface were prepared by establishing a rough structure on the surface of silica (SiO₂) modified with silane coupling agents (γ‐(2,3‐epoxypropoxy)propytrimethoxysilane (KH560) and (heptadecafluoro‐1,1,2,2‐tetradecyl)trimethoxysilane (FAS)). First, the surface of SiO₂ was covered by a layer of hydrophobic methyl and fluorocarbon (C–F) groups. Then, the SiO₂ and modified SiO₂ were obtained by the introduction of KH560 and FAS with the silanol reaction by ultrasonic stirring. The effect of SiO₂ and modified SiO₂ on the structure and hydrophobic properties of PU was investigated by a series of test instruments. The results showed that the introduction of SiO₂ and modified SiO₂ was beneficial for increasing the roughness of the PU coating surface; the roughness of FAS/SiO₂‐PU could reach up to 14.790 nm, four times better than pure PU. A hydrophobic modified PU coating with water contact angle 123° was fabricated by using the hydrophobic C–F group FAS as a low surface energy material and establishing a micro rough structure on the surface of PU. Moreover, PU modified with KH560 and FAS can reduce the glass transition temperature (T_g) of soft segments, resulting in improvement of micro‐phase separation. © 2020 Society of Chemical Industry     

Effects on the structure and properties of membranes formed by blending polydimethylsiloxane polyurethane into different soft‐segment waterborne polyurethanes

Polydimethylsiloxane polyurethane (PDMS‐PU), which was synthesized from PDMS as the soft segment, was blended into a variety of ester‐ or ether‐based soft‐segment waterborne polyurethanes with different concentrations to investigate the crystallization, thermal, and physical properties of the membrane formations. According to X‐ray analysis, the ether‐based PUs, synthesized from soft segments of poly(propylene glycol) (PPG1000) or poly(ethylene glycol) (PEG2000), were found to have maximum crystallinity at a 5% blending ratio of PDMS‐PU, but the ester‐based PU, synthesized from soft segments of polycaprolactone (PCL1250), had decreased crystallinity at a 5% blending ratio. Differential scanning calorimetric analysis revealed that the T_g,s values of PUs were highest when the blending ratio of PDMS‐PU was 5%–10%, except for PU from PCL1250. Moreover, ether‐based PUs showed maximum T_m,h values, but the T_m,h of the ester‐based PU was greatly reduced when PU with PCL1250 was blended with PDMS‐PU. In addition, the PU from PEG2000 had the highest melting entropy. Mechanical property analysis showed that the stress of ether‐based PUs would be increased when PUs were blended with a small amount of PDMS‐PU and that the stress of PU from poly(tetramethylene glycol) (PTMG1000) increased to its greatest value (20–30 MPa). On the other hand, the ester‐based PU, from PCL1250 blended with PDMS‐PU, would have reduced stress. On the whole, the stress and strain of PU from PEG1000 had excellent balance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 210–221, 2006     

Synthesis of a polydimethylsiloxane-block-hydroxyl grafted acrylate prepolymer copolymer to improve the adhesion between silicone rubber and polyurethane by induced surface reconstruction

A new class of hydroxyl-functionalized polydimethylsiloxane-block-hydroxyl graft acrylate prepolymer (PDMS-b-HGAP) copolymers was synthesized. The copolymers were characterized using Fourier transform infrared spectroscopy as well as ¹H and ¹³C nuclear magnetic resonance spectroscopy. The hydroxyl groups of the HGAP were reacted with the chlorine terminal in the PDMS to yield a triblock copolymer consisting of two segments of PDMS linked to a HGAP segment. The induced surface reconstruction of silicone rubber (SR)by blending polysiloxane reactants with bifunctional PDMS-b-HGAP copolymers and curing using mold materials having high critical surface tension such as polyethyleneterephthalate was attempted to improve the adhesion between chemically-inert SR and polyurethane (PU). Surface characterization using Foruier transform infrared-attenuated total reflectance indicated that the surface of the SR was enriched with HGAP. The increased content of surface HGAP was suggested to account for the improved adhesion between SR and PU.     

Synthesis and CO2 separation of novel polyurethane membranes containing urea linkages

We synthesized novel polyurethane (PU) membranes from isophorone diisocyanate (IPDI), poly(ethylene glycol) (PEG) with a molecular weight of 2000, aminopropyl-terminated poly(dimethyl siloxane) (PDMS) with a molecular weight of 2000, and 1,4-butanediol (BDO) via a two-step polymerization. The structure of each synthesized membrane was studied through Fourier transform infrared spectroscopy and gel permeation chromatography. The effect of the thermal behavior was determined by differential scanning calorimetry and thermogravimetric analysis. The gas-permeability characteristics of the PU membranes were then tested for a single gas. The results show that the permeability of CO₂ (P_CO2) gradually increased with PDMS content. Among these PU membranes, PU-d (PEG/PDMS = 1:1, PEG/PDMS/IPDI/BDO = 1:3:2) showed the best P_CO2 (132.6 Barrer) at 25°C and 1 bar pressure. The gas-permeability coefficients of each PU membrane at different operating temperatures were investigated, and the results show that P_CO2 reached 302.6 Barrer at 65°C and 1 bar. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47723.     

Comparison of the effects of linking diglycidyl ether‐terminated PDMS and BPA onto polyurethane with respect to the tensile and thermal properties

Flexible poly(dimethylsiloxane) (PDMS) or rigid bisphenol A (BPA) with diglycidyl ether end groups was linked to polyurethane (PU), which was composed of 4,4′‐methylenebis(phenyl isocyanate) as a hard segment and poly(tetramethylene ether)glycol as a soft segment. A control PDMS (CPDMS) series was prepared with an additional deprotonation step by NaH. The spectroscopic, thermal, tensile, shape memory, and low‐temperature flexibility properties were compared with those of plain PU to investigate the effects of linking the flexible PDMS or the rigid BPA on PU. The soft segment melting peaks were not affected by the PDMS content for the PDMS series but disappeared as the BPA content increased in the BPA series. The soft segment crystallization of PU was completely disrupted as the linked BPA content increased in the differential scanning calorimetry results and disappeared in the dynamic mechanical analysis results. The glass transition temperature (T_g) of the BPA series increased with increasing BPA content, whereas that of the PDMS series remained the same. The tensile strength of the PDMS series sharply increased with increasing PDMS content. The shape retention of the BPA series at ?25 °C sharply decreased as the BPA content increased. Finally, the BPA series linked with rigid aromatic BPA demonstrated excellent low‐temperature flexibilities compared with the PDMS series and plain PU. Compared with PUs linked with PDMS, PUs linked with rigid BPA demonstrated a significant change in the cross‐link density, thermal properties, shape retention, and low‐temperature flexibility. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43284.     

Preparation and evaluation of hydrophobic surfaces of polyacrylate-polydimethylsiloxane copolymers for anti-icing

Two series of polyacrylate-polydimethylsiloxane (PDMS) copolymers, namely, polyacrylate-b-PDMS and polyacrylate-g-PDMS with three different molecular weights of PDMS blocks or side chains, were synthesized for formation of hydrophobic surfaces for anti-icing. The main purpose of this paper was to investigate the relationship between ice adhesion strength and the surface structure of the copolymers, and to find out how the prepared PDMS-containing polyacrylate copolymers are potentially used for anti-icing. The microphase-separated structure and the surface chemical composition were analyzed by transmission electron microscopy, atomic force microscopy and X-ray photoelectron spectroscopy, and ice adhesion strength was measured using a universal testing machine in a pull off mode. Results suggested that microphase separation appeared clearly in all the copolymers, especially for the block ones. The PDMS chains aggregated on the top of the polymer surfaces caused by microphase separation could weaken the interaction between the polymer surface and water, mainly hydrogen bond, which was demonstrated because of decrease of water contact angle hysteresis. Then, ice adhesion strength was decreased by the contribution of PDMS in the block copolymers or the graft copolymer with longer PDMS side chains. It is suggested that the polyacrylate-b-PDMS or polyacrylate-g-PDMS copolymers would have practical applications in preparation of anti-icing coatings.     

Dielectric and thermal studies of segmental dynamics in silica/PDMS and silica/titania/PDMS nanocomposites

Effects of silica and silica/titania nanoparticles on glass transition and segmental dynamics of poly(dimethylsiloxane) (PDMS) were studied for composites of a core–shell type using differential scanning calorimetry, thermally stimulated depolarization current, and dielectric relaxation spectroscopy techniques. Strong interactions between the filler and the polymer suppress crystallinity (T_c, X_c) and affect significantly the evolution of the glass transition in the nanocomposites. The segmental relaxation associated with the glass transition consists of three contributions, arising, in the order of decreasing mobility, from the bulk (unaffected) amorphous polymer fraction (α relaxation), from polymer chains restricted between condensed crystal regions (α_c relaxation), and from the semi‐bound polymers in an interfacial layer with strongly reduced mobility due to interactions with surface hydroxyls of silica and silica/titania nanoparticles (α′ relaxation). The evolution of surface affected CH₃ groups, as well as the degree of interaction of PDMS molecules with surface hydroxyl groups as a function of treatment temperature, was assessed by Fourier transform infrared spectroscopy, thermogravimetry and differential thermal analysis. The effectiveness of silica/PDMS and silica/titania/PDMS nanocomposites as hydrophobic coatings was investigated by static contact angle measurements. It was shown that the presence of titania nanoparticles and adsorbed PDMS promotes the hydrophobic properties of the PDMS coating after treatment in the 80–650°C range. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41154.     

Synthesis and characterizations of waterborne polyurethane modified with 3-aminopropyltriethoxysilane

Waterborne polyurethane (WPU) was prepared by the reaction of isophorone isocyanate (IPDI), polyether polyol (PTMG1000), dimethylol propionic acid (DMPA), and trimethylol propane (TMP) and 3-aminopropyltriethoxysilane (APTES) as coupling agent. The films of the WPU were prepared by casting emulsions on Teflon surfaces. The structure of the polyurethane (PU) was characterized by Fourier transform infrared spectrometer (FT-IR), thermogravimetry (TG), X-ray diffraction (XRD), and differential scanning calorimeter (DSC). The mechanical properties and solvent absorption of the cast films were also measured quantificationally. FT-IR indicates that –NH₂ of APTES reacted with –NCO of PU prepolymer. TG analysis indicates that APTES can improve thermal stability of PU. XRD and DSC show that crystallinity of PU decreased with the increase of w(APTES). It was found that greater mechanical properties of WPU were obtained when chemical networks were formed between PU and APTES. As the mass fraction of APTES increases from 0% to 10%, water absorption decreased from 17% to 8%, ethanol absorption decreased from 46% to 30%. The particle size increases with increase of w(APTES).     

Preparation of waterborne polyurethanes using an amphiphilic diol for breathable waterproof textile coatings

The application of polyurethanes (PUs) on breathable waterproof fabric coatings requires a balance of water vapor permeability (WVP) and water resistance which can be achieved by tailoring hydrophilic and hydrophobic segments. PU prepolymers were prepared from isophorone diisocyanate, dimethylol butanoic acid, and a mixture of various ratios of amphiphilic PPG2050 (copolymer of ethylene oxide and propylene oxide with –OH end groups) and hydrophobic poly(tetramethylene ether glycol) (PTMEG). After neutralization with triethylamine, the prepolymers were chain-extended with ethylene diamine/1,4-butanediol (1:1 by molar). The WVP values of the fabric coatings prepared using various waterborne PUs were very similar (910–990 g/m² × 24 h). When waterborne PUs prepared using a mixture of PPG2050 and PTMEG were employed for the textile coatings, the resulting PU-coated textiles exhibited excellent waterproof properties (>10,000 mm H₂O). The textile coatings prepared from PPG2050/PTMEG-based waterborne PUs were significantly more waterproof than those prepared from poly(ethylene glycol) (PEG)/poly(propylene glycol) (PPG)/PTMEG-based waterborne PU. This is probably due to a more even distribution of hydrophobic segments in the PUs, even though the WVP values of the PEG/PPG/PTMEG-based PU coatings were considerably smaller than those of the PPG2050/PTMEG-based PU coatings.     

A polycaprolactone‐based compatibilization treatment to improve dispersion and interphase structure of silica polyurethane composites

Silica nanoparticles (SNs) were grafted with ε ‐caprolactone using an environmentally friendly approach. By using tartaric acid as a catalyst and the silanol groups as initiators, grafted nanoparticles (GNs) with organic weight fractions (w_of) within the range 0–46 wt% were synthesized. Thermogravimetric (TGA) and infrared analysis were used to measure the w_of and to corroborate the covalent bond between the SN and the caprolactone monomer. Transmission electron micrographs of the polyurethane (PU) nanocomposites based on the SN and the GN revealed that the interfacial area of the GN‐based PU increased by the reduction of agglomerate dimensions from 10 µm to around 0.1 µm. Dynamic mechanical analysis showed that the GN nanocomposites improved the storage shear modulus from 616±11 to 849±8 MPa for a GN with w_of = 16.7% and 3 wt% filler concentration. In addition, the GN particles prevented a relevant decrease of the transition temperature (T_g). Differential scanning calorimetry corroborated that GN increased the enthalpic energy associated to the physical crosslinking of the hard segments (HS). Wide‐angle X‐ray diffraction proved that the GN formed a HS structure with improved crystallinity. The thermal stability of the GN‐based PU a nanocomposite was improved by an increase of the thermal stability of the castor oil soft segments. POLYM. ENG. SCI., 54:1817–1826, 2014. © 2013 Society of Plastics Engineers     

Preparation of waterborne polyurethanes using an amphiphilic diol for breathable waterproof textile coatings

The application of polyurethanes (PUs) on breathable waterproof fabric coatings requires a balance of water vapor permeability (WVP) and water resistance which can be achieved by tailoring hydrophilic and hydrophobic segments. PU prepolymers were prepared from isophorone diisocyanate, dimethylol butanoic acid, and a mixture of various ratios of amphiphilic PPG2050 (copolymer of ethylene oxide and propylene oxide with –OH end groups) and hydrophobic poly(tetramethylene ether glycol) (PTMEG). After neutralization with triethylamine, the prepolymers were chain-extended with ethylene diamine/1,4-butanediol (1:1 by molar). The WVP values of the fabric coatings prepared using various waterborne PUs were very similar (910–990 g/m² × 24 h). When waterborne PUs prepared using a mixture of PPG2050 and PTMEG were employed for the textile coatings, the resulting PU-coated textiles exhibited excellent waterproof properties (>10,000 mm H₂O). The textile coatings prepared from PPG2050/PTMEG-based waterborne PUs were significantly more waterproof than those prepared from poly(ethylene glycol) (PEG)/poly(propylene glycol) (PPG)/PTMEG-based waterborne PU. This is probably due to a more even distribution of hydrophobic segments in the PUs, even though the WVP values of the PEG/PPG/PTMEG-based PU coatings were considerably smaller than those of the PPG2050/PTMEG-based PU coatings.     

Study on polyethylene glycol/polydimethylsiloxane mixing soft‐segment waterborne polyurethane from different mixing processes

The surface structure and physical properties of polyethylene glycol series polyurethane (PEG‐PU) membranes, in which were introduced hydrophobic polydimethylsiloxane (PDMS) component by the procedure of PU blending or of soft‐segment copolymerization, were studied in this investigation. In the case of the blending process, the synthesized waterborne polyurethanes (WBPUs) of PEG–PU and of polydimethylsiloxane series polyurethane (PDMS–PU) were combined, whereas in the copolymerization process PEG and PDMS were taken as mixed soft segments to polymerize the WBPU. For the blending method, glass‐transition and melting temperatures increased rapidly when a small amount of PDMS–PU was added to PEG–PU and reached a maximum with 5% PDMS–PU mixed in. However, in the case of the copolymer method, thermal properties closely followed predicted values. From dynamic mechanical analysis studies it was found that a low PDMS–PU content ratio could increase the rubbery elasticity of PEG–PU membrane and improve its strength simultaneously in the blending method, and the copolymer method only caused PU to gain some natural complementary strength and elasticity. Electron spectroscopy for chemical analysis studies indicated that PDMS migrated to the surface much more easily in the blending method than in the copolymer method. The SEM studies also found that, in the blending method, the numbers of pores were less than those in the copolymer method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 233–243, 2003     

Polydimethylsiloxane based polyurethane and its composite with layered double hydroxide: Synthesis and its thermal properties

This investigation reports the synthesis of a new class of polyurethane (PU) based on bis(hydroxyalkyl) polydimethylsiloxane (PDMS) as diol and isophorone diisocyanate as diisocyanate followed by the preparation of PU/layered double hydroxide (PU/LDH) nanocomposite via ex-situ technique. Nuclear magnetic resonance and Fourier-transform infrared spectroscopy studies confirm the formation of PU and incorporation of PDMS into the PU backbone. Thermogravimetry analysis revealed that thermal stability of the composite improves significantly with incorporation of LDH into the PU matrix. This may be accredited to the barrier effect rendered by the LDH layers. Differential scanning calorimetry study reveals that with the incorporation of LDH, glass transition temperature (T_g) of the composite increases for an optimum level of loading beyond which it remains constant.     

Improved adhesion of silicone rubber to polyurethane by induced surface reconstruction

Induced surface reconstruction of silicone rubber by blending polydimethylsiloxane (PDMS) reactants with bifunctional PDMS-hydroxyl terminated polybutadiene (PDMS-b-HTPB) copolymers and curing with appropriate mold material was attempted to improve the adhesion of chemically inert silicone rubber to polyurethane (PU). Surface characterization using Fourier transform infrared-attenuated total reflectance indicated that the surface of the silicone rubber possessed a controlled amount of HTPB. The surface was enriched with HTPB by using mold materials having high critical surface tension, such as aluminum. A dynamic surface rearrangement occurred during a 1-h heating cycle at 70°C, changing from an HTPB-enriched surface to a PDMS-enriched surface. The peel strength between the silicone rubber and PU was found to increase with decreased propanol residue and with an increase in critical surface tension of the molding materials. The increased content of surface HTPB was suggested to account for the improved adhesion of silicone rubber to PU. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1669–1675, 1998     

Influence of ionic groups on the crystallization and melting behavior of segmented polyurethane ionomers

The isothermal crystallization kinetics and melting behavior of the soft segment in polyurethane (PU) ionomer/nonionomer based on PCL‐4000 (poly(ε‐caprolactone)) were investigated using polarizing optical microscopy (POM) and differential scanning calorimetry (DSC). In general, the presence of ionic groups in PU ionomers can promote the formation of a more stable crystalline structure and lower the equilibrium melting temperature of the crystallizable phase. Comparison between the crystallization characteristics of PU nonionomers and ionomers suggests that the Coulombic Forces between ionic groups within hard segment can increase the crystallization rate and decrease the crystal size of soft segment when the total molecular weight (M_w) of PU ionomer is higher than ～71,000. On the other hand, the opposite effect of ionic groups on the crystallization rate is observed in PU ionomers with M_w below ～20,000. The DSC thermograms illustrate that the ionic groups can significantly enhance the microphase separation in PU ionomers with higher M_w values. By the control and manipulation of crystallization and microstructure formation in PU ionomer, it is possible to achieve shape memory PUs with superior physical property. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4603–4613, 2006     

Enhancement of mechanical and optical performance of commercial polystyrenes by blending with siloxane‐based copolymers

Well‐defined poly(styrene‐block ‐dimethylsiloxane) copolymers (PS‐b ‐PDMS) with low polydispersity index (M_w /M_n ) and different compositions were synthesized by sequential anionic polymerization of styrene (S) and hexamethyl(ciclotrisiloxane) (D₃) monomers. Synthesized PS‐b ‐PDMS copolymers were characterized by ¹H‐nuclear magnetic resonance, size exclusion chromatography, Fourier transform infrared spectroscopy, and transmission electron microscopy. The physicochemical characterization determined that block copolymers have molar mass values close to ～135,000 g mol^?1, narrow M_w /M_n < 1.3, and chemical composition ranging from low to intermediate PDMS content. Blends of these copolymers with a commercial polystyrene (PS) were obtained by melt mixing and subsequently injection. Films obtained were flexible, and showed lower transparency than the original PS matrix. On the other hand, a 10 wt % incorporation of PS‐b ‐PDMS copolymers leads to better mechanical performance by enhancing elongation at break (～8.8 times higher) and opacity values (～18 times higher). In addition, UV–Vis barrier capacity of the resulting blends is also increased (up to 400% higher). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45122.     

Modification of polydimethylsiloxane with polyvinylpyrrolidone: Influence of reinforcing filler on physico‐mechanical properties

The present article reports an approach for the modification of hydrophobic polydimethylsiloxane (PDMS) with low molecular weight hydrophilic polyvinylpyrrolidone (PVP) via solution blending method to develop new PDMS‐based materials with improved mechanical performance and wettability which can be used in many biomedical applications. The influence of dimethyldichlorosilane treated fumed silica (FS) on physico‐mechanical properties of PDMS–PVP blends were investigated and analyzed. There was the significant improvement in mechanical, dynamic mechanical and thermal properties of PDMS–PVP blends, whereas, transparency and contact angle were slightly decreased after incorporation of FS into PDMS–PVP blends. Scanning electron microscopy revealed that the fourfold reduction in the average domain size of the dispersed PVP in the PDMS matrix in the presence of compatibilizer (PDMS‐PEO block copolymer) when compared with the uncompatibilized PDMS–PVP blend morphology. By incorporation of FS into the neat PDMS matrix, the onset of degradation (T_i), the maximum rate of degradation (T_max) and overall thermal stabilities increased significantly. On the other hand, by the addition of FS into to PDMS–PVP blends, the T_i and T_max remains unaffected, but overall thermal stabilities increased significantly. PDMS–PVP blends exhibited low contact angle (～45°) which confirmed the formation of the hydrophilic surface. POLYM. ENG. SCI., 56:491–499, 2016. © 2016 Society of Plastics Engineers     

Effects of simultaneous chemical cross-linking and physical filling on separation performances of PU membranes

The novel modified polyurethane (PU) membranes were prepared by β-cyclodextrin (CD) cross-linking and SiO₂/carbon fiber filler, simultaneously. The structures, thermal stabilities, morphologies, and surface properties were characterized by FTIR, TGA, SEM, and contact angle. The results showed that the addition of inorganic particles increased the thermal stabilities of PU membranes. The modified PU membranes possessed more hydrophobic surfaces than pure PU. In the swelling investigation, PU and its modified membranes were swelled gradually with increasing phenol content in the mixture. The membranes modified by CD cross-linking (PUCD) demonstrated the highest swelling degree. Pervaporation (PV) performances were investigated in the separation of phenol from water. Three kinds of modified membranes obtained better permeability and selectivity than PU membranes. With the feed mixture of 0.5 wt% phenol at 60 °C, the modified PU membrane by CD cross-linking and SiO₂ filler (PUCD-S) obtained the total flux of 5.92 kg μm m^?2 h^?1 which was above doubled that of PU (2.90 kg μm m^?2 h^?1). The modified PU membrane by CD cross-linking and carbon fiber filling (PUCD-C) obtained the separation factor of 51.31 which was nearly tripled that of PU (17.72). The PUCD membranes showed both better permeability and selectivity than the pure PU membranes. The increased phenol content induced an increased separation factor of PUCD and PU, but a decreased selectivity of PUCD-S and PUCD-C. The methods of CD cross-linking and inorganic particle filling were effective to develop the overall separation performances, greatly.     

HTPB‐based polyurethaneurea membranes for recovery of aroma compounds from aqueous solution by pervaporation

Hydroxyterminated polybutadiene (HTPB)‐based polyurethaneurea (PU), HTPB‐PU, was synthesized by two‐step polymerization and was firstly used as membrane materials to recover aroma, ethyl acetate (EA), from aqueous solution by pervaporation (PV). The effects of the number–average molecular weight (M_n) of HTPB, EA in feed, operating temperature, and membrane thickness on the PV performance of HTPB‐PU membranes were investigated. The membranes demonstrated high EA permselectivity as well as high EA flux. The DSC result showed two transition temperatures in the HTPB‐PU membrane and contact angle measurements revealed the difference of hydrophobicity of the membrane at both sides, which were induced by glass plate and air, respectively, due to movement of the soft hydrophobic polybutadiene (PB) segments in HTPB‐PU chains. Furthermore, the PV performance of the HTPB‐PU membrane with the hydrophobic surface facing the feed was much better than that with the hydrophilic surface. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 552–559, 2007