Molecular transport of n‐alkanes into PU/PBMA interpenetrating polymer network systems

The methylene diisocyanate (MDI) and toluene diisocyanate (TDI) based polyurethane/polybutyl methacrylate (PU/PBMA‐50/50) interpenetrating polymer network (IPN) membranes have been prepared. The molecular migration of n‐alkane penetrants such as hexane, heptane, octane, nonane, and decane through PU/PBMA (50/50) membranes has been studied at 25, 40, and 60°C using a weight gain method. From the sorption results, diffusion (D) and permeation (P) coefficients of n‐alkane penetrants have been calculated. Molecular migration depends on membrane‐solvent interactions, size of the penetrants, temperature, and availability of free volume within the membrane matrix. Attempts have been made to estimate the parameters of an empirical equation and these data suggest that molecular transport follows Fickian mode. From a study of temperature dependence of transport parameters, activation energy for diffusion (E_D) and permeation (E_P) have been estimated from the Arrhenius relation. Furthermore, sorption results have been interpreted in terms of enthalpy (ΔH) and entropy (ΔS) of sorption. The liquid concentration profiles have been computed using Fick's equation with appropriate initial and boundary conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 739–746, 2003     

Free volume and the physico‐mechanical behaviour of polyurethane/polyacrylonitrile interpenetrating polymer networks: positron annihilation results

A series of semi‐interpenetrating polymer networks (SIPNs) of polyurethane (PU) and polyacrylonitrile (PAN) in the weight ratios 90/10, 70/30, 60/40 and 50/50 PU/PAN were prepared using polyethylene glycol, 4,4′‐diphenylmethane diisocyanate and acrylonitrile by sequential polymerization. Differential scanning calorimetry and scanning electron microscopy techniques were used to find the glass transition temperature and surface morphology of SIPNs. The tough and transparent SIPN films were characterized for physico‐mechanical properties such as density, surface hardness and tensile properties. Positron annihilation lifetime spectroscopy (PALS) was used to measure the free volume behaviour of the IPNs. The sorption behaviour of IPNs with benzene penetrant was also measured. An attempt was made to correlate the PALS results with the mechanical and sorption properties of the SIPNs. Copyright © 2005 Society of Chemical Industry     

Castor oil‐based polyurethane–polyester nonwoven fabric composites: Mechanical properties,chemical resistance,and water sorption behavior at different temperatures

Castor oil‐based polyurethane (PU)–polyester nonwoven fabric composites were fabricated by impregnating the polyester nonwoven fabric in a composition containing castor oil and diisocyanate. The effects of different diisocyanates such as toluene‐2,4‐diisocyanate (TDI) and hexamethylene diisocyanate (HMDI) on the mechanical properties have been studied for neat PU sheets and their composites with polyester nonwoven fabric. Chemical resistance of the PU composites has been assessed by exposing the specimens to different chemical environments. Percentage water absorption of composites and neat PU sheets has been determined both at room temperature and in boiling water. Both TDI‐ and HMDI‐based PU composites showed a marginal improvement in tensile strength retention at 100°C heat ageing. Water sorption studies were carried out at different temperatures, viz, 30, 50, and 70°C, based on immersion weight gain method. From the sorption results, the diffusion (D) and permeation (P) coefficients of water penetrant have been calculated. Attempts were made to estimate the empirical parameters such as n, which suggests the mode of transport (non‐Fickian), and K, a constant which depends on the structural characteristics of the polymer in addition to its interaction in boiling water. The temperature dependence of the transport coefficients has been used to estimate the activation energy parameters for diffusion (E_D) and permeation (E_p) processes from Arrhenius plots. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Nano‐SiO2/PMMA‐PU composite particles with core‐shell structure via emulsion polymerization and their application in epoxy resin

A novel method of nano‐SiO₂/poly(methyl methacrylate)(PMMA)‐polyurethane(PU) composite particles modifying epoxy resin is reported. The composite particles with the obvious core‐shell structure were prepared by emulsion polymerization of PMMA and PU prepolymer on the surface of nano‐SiO₂. The diameter of the composite particles was 50–100 nm with dark core SiO₂ (30–60 nm) and light shell polymer of PMMA and PU (20–30 nm); moreover, PU was well distributed in PMMA with about 10 nm diameter. After nano‐SiO₂ was encapsulated by PMMA and PU, the Si content on the surface decreased rapidly to 2.08% and the N content introduced by PU was about 1.27%. The ratio of polymer to original nano‐SiO₂ (f_p), the grafting ratio of polymer to original nano‐SiO₂ (f_r) and the efficiency grafting ratio of polymer (f_e) were, respectively, about 116.7%, 104.4%, and 89.5%. The as‐prepared composite particles were an effective toughness agent to modify epoxy resin, and the impact strength of the modified epoxy resin increased to 46.64 kJ m^?2 from 19.12 kJ m^?2 of the neat epoxy resin. This research may enrich the field of inorganic nanoparticles with important advances toward the modification for polymer composite materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41919.     

Effect of propylene carbonate on the ionic conductivity of polyacrylonitrile‐based solid polymer electrolytes

Solid polymer electrolyte membranes consisting of polyacrylonitrile (PAN) as a host polymer, ammonium nitrate (NH₄NO₃) as a complexing salt, and propylene carbonate (PC) as a plasticizer were prepared by a solution casting technique. An increase in the amorphous nature of the polymer electrolytes was confirmed by X‐ray diffraction analysis. A shift in the glass‐transition temperature of the PAN/NH₄NO₃/PC electrolytes was observed in the differential scanning calorimetry thermograms; this indicated interactions between the polymer and the salt. The impedance spectroscopy technique was used to study the mode of ion conduction in the plasticized polymer electrolyte. The highest ionic conductivity was found to be 7.48 × 10^?3 S/cm at 303 K for 80 mol % PAN, 20 mol % NH₄NO₃, and 0.02 mol % PC. The activation energy of the plasticized polymer electrolyte (80 mol % PAN/20 mol % NH₄NO₃/0.02 mol % PC) was found to be 0.08 eV; this was considerably lower than that of the film without the plasticizers. The dielectric behavior of the electrolyte is discussed in this article. A literature survey indicated that the synthesis and characterization of ammonium‐salt‐doped, proton‐conducting polymer electrolytes based on PAN has been rare. The use of the best composition membrane (80 mol % PAN/20 mol % NH₄NO₃/0.02 mol % PC) proton battery was constructed and evaluated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41743.     

Schiff base‐substituted polyphenol: synthesis,characterisation and non‐isothermal degradation kinetics

BACKGROUND: Polymers of phenols and aromatic amines have emerged as new materials in fields such as superconductors, coatings, laminates, photoresists and high‐temperature environments. The stability, kinetics and associated pollution of the thermal decomposition of oligophenols are of interest for the aforementioned fields. RESULTS: A new Schiff base polymer, derived from N,N′‐bis(2‐hydroxy‐3‐methoxyphenylmethylidene)‐2,6‐pyridinediamine, was prepared by oxidative polycondensation. Characterisations using Fourier transform infrared, UV‐visible, ¹H NMR and ¹³C NMR spectroscopy, thermogravimetric/differential thermal analysis, gel permeation chromatography, cyclic voltammetry and conductivity measurements were performed. The number‐average (M_n) and weight‐average molecular weight (M_w) and dispersity (D = M_w/M_n) of the polymer were found to be 61 000 and 94 200 g mol^?1 and 1.54, respectively. Apparent activation energies of the thermal decomposition of the polymer were determined using the Tang, Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose and Coats–Redfern methods. The most likely decomposition process was a D_n deceleration type in terms of the Coats–Redfern and master plot results. CONCLUSION: The mechanism of the degradation process can be understood through the use of kinetic parameters obtained from various non‐isothermal methods. Copyright © 2009 Society of Chemical Industry     

Polyurethanes from 4,4′‐diphenylmethane diisocyanate and poly(ethylene glycol)s. II. Crystallographic data,heats of melting and crystallization,thermal stability,crystallinity and density

Wide‐angle X‐ray scattering analysis, heats of melting, crystallization and re‐melting, thermogravimetric analysis and density measurements have been used to study the crystallographic data and degree of crystallinity of linear polyurethanes (PUs) prepared by the polymerization of 4,4′‐diphenylmethane diisocyanate (MDI) with poly(ethylene glycol)s (PEGs) of various number‐average molecular weights (M_ns) (106, 200, 400, 1000, 2000 and 4000 g mol^?1) in equivalent molar ratios. The crystallinities of polyurethanes PU1000 to PU4000 are shown to be due to the polyoxyethylene segments of the PEGs, while PU400 and PU200 appeared to be amorphous. However, PU106, similarly prepared from diethylene glycol (PEG106), is highly crystalline with a different crystal structure. Thermogravimetric analysis of PU106, PU400 and PU1000 exhibited high thermal stabilities up to 260 °C for these materials under the conditions of measurement (10 °C min^?1). The heat of melting for the 100 % crystalline structure of PU106 has been indirectly obtained. Copyright © 2004 Society of Chemical Industry     

Semicontinuous emulsion copolymerization of 3‐O‐methacryloyl‐1,2:5,6‐di‐O‐isopropylidene‐α‐D‐glucofuranose (3‐MDG) and butyl acrylate (BA). Monomer feed addition

New polymer colloids based on the saccharide monomer, using of 3‐O‐methacryloyl‐1,2:5,6‐di‐O‐isopropylidene‐α‐D ‐glucofuranose (3‐MDG), were prepared by semicontinuous emulsion polymerization, a widely used industrial process. The copolymerization of 3‐MDG and butyl acrylate (BA), by the monomer‐addition technique, at 70°C, using sodium persulfate (Na₂S₂O₈) as an initiator, was investigated. The influence of some reaction parameters, such as the type and concentration of the surfactants as well as the monomer addition rate (R_m) on the polymerization rate (R_p), the colloidal properties, and the stability of the latexes, was studied. It was found that under starved‐feed conditions the polymerization rate and the particle size (D) increased with an increasing rate of monomer addition. The weight‐average molecular weight (M _w) also increased by enhancing R_m and a narrower molecular weight distribution was obtained. Furthermore, the type and the concentration of the surfactants strongly influenced the particle size and its distribution. The effect of the seed stage on the particle size and its distribution was also investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2091–2102, 2003     

Synthesis,characterization, and mechanical property of poly(urethane‐glycidyl methacrylate‐methyl methacrylate) hybrid polymers

Hybrid particles of polyurethane (PU) containing a number of small poly(methyl methacrylate) (PMMA) nanoparticles inside were prepared using glycidyl methacrylate (GMA) monomer as a linker between PU and PMMA; the resulting polymers were poly (urethane‐glycidyl methacrylate‐methyl methacrylate) (PUGM). It was found that the average particle size (D_p) of the PU particles decreased by the inclusion of PMMA particles possibly owing to the low‐solution viscosity of PU. However, D_p of the PUGM hybrid particles increased with increasing the number of covalent bonds between PMMA and PU, which might be due to decreasing the amount of ionic groups per PU chain. Subsequently, the tensile properties of the films made of the PUGM hybrid particles were investigated. It was observed that the modulus of the PU films increased upon the addition of PMMA particle because of a filler effect. In addition, it was seen that the modulus of PUGM hybrid films increased further with increasing the number of covalent bonds. This was attributed to “restricted mobility” of PU chains anchored to the PMMA particles. It was also observed that the tensile strength changed only slightly for PUGM particles, suggesting that the PU matrix was probably responsible for the necking behavior of the films. The elongation of the samples was found to depend on both the presence of covalent bonds between the PMMA particles and PU matrix and the reduced mobility of the PU chains anchored to PMMA particles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and ionic conductive properties of polydioxolane–polyurethane‐based electrolytes

A series of polyurethanes (PUs) with different polyether soft segments [polydioxolane (PDXL), polyethylene glycol (PEG), or PDXL/PEG] were synthesized successfully, and solid polymer electrolytes based on PU/LiClO₄ complexes were prepared. The relations between structure and the ionic conductive properties of the PU‐based electrolytes were investigated by means of Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, and complex impedance analysis. Results showed that the glass‐transition temperature (T_g) of PDXL–PU was lower than that of PEG–PU. Doped lithium perchlorate (LiClO₄) salt could be dissolved well in soft segments of PDXL–PU. The ionic conductivity of the PDXL–PU/LiClO₄ complex could reach a value of 2 × 10^?5 S/cm at room temperature without the addition of an organic plasticizer. The system with PDXL/PEG as a soft segment had a higher T_g and a lower ionic conductivity than the one with PDXL as a soft segment. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 103–111, 2002     

Raman spectroscopic study of the microstructure of carbon films developed from cobalt chloride‐modified polyacrylonitrile

Polyacrylonitrile (PAN) was modified with cobalt chloride at 90°C for 5 min. The carbon films prepared from original and modified PAN films were carbonized up to 1300°C. The structure of the resulting carbon film was studied using X‐ray diffraction and Raman spectroscopy. The stacking size obtained from X‐ray diffraction approaches the L_c value of the resulting carbon films as the heat treatment temperature increased. The mean average carbon basal planes in crystalline (Lc/d) also increased with increasing pyrolysis temperature. Raman spectra confirmed the progressive structural ordering as treatment temperature increased. During pyrolysis, a substantial decrease in the intensity of the band near the 1350 cm⁻¹ region was observed, indicating a decrease in the disordered structure. The crystal size (L_a) of the resulting carbon films also showed a remarkable increase with increased heat treatment temperature. The resulting carbon films developed from the modified PAN films had higher L_c and L_a than those developed from the original PAN film. It was established that cobalt catalyzes graphitization of amorphous carbon during pyrolysis. This modification not only promoted the growth of crystal size but also increased the close packing of the carbon basal planes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2219–2225, 1999     

Synthesis,characterization and properties of organoclay‐modified polyurethane/epoxy interpenetrating polymer network nanocomposites

organoclay‐modified polyurethane/epoxy interpenetrating network nanocomposites (oM‐PU/EP nanocomposites) were prepared by adding organophilic montmorillonite (oMMT) to interpenetrating polymer networks (IPNs) of polyurethane and epoxy resin (PU/EP) which had been prepared by a sequential polymerization technique. Wide‐angle X‐ray diffraction (WAXD) and transmission electronic microscopy (TEM) analysis showed that the interpenetrating process of PU and EP improved the exfoliation and dispersion degree of oMMT. The effects of the NCO/OH ratio (isocyanate index), the weight ratio of PU/EP and oMMT content on the phase structure and the mechanical properties of the oM‐PU/EP nanocomposites were studied by tensile testing and scanning electronic microscopy (SEM). Water absorption tests showed that the PU/EP interpenetrating networks and oMMT had synergistic effects on improvement in the water resistance of the oM‐PU/EP nanocomposites. Differential scanning calorimetry (DSC) analysis showed that PU was compatible with EP and that the glass transition temperature (T_g) of the oM‐PU/EP nanocomposites increased with the oMMT content up to 3 wt%, and then decreased with further increasing oMMT content. The thermal stability of these nanocomposites with various oMMT contents was studied by thermogravimetric analysis (TGA), and the mechanism of thermal stability improvement was discussed according to the experimental results. Copyright © 2005 Society of Chemical Industry     

Carbon fibers derived from wet‐spinning of equi‐component lignin/polyacrylonitrile blends

Equi‐component blends of polyacrylonitrile (PAN) and lignin, i.e., with a lignin content as large as 50 wt %, were successfully used as precursors to produce carbon fibers. Rheological measurements demonstrated that increasing lignin content in spinning solution reduced shear viscosity and normal stress, indicating a decrease of viscoelastic behavior. This was confirmed by Fourier transform infrared results that show no discernable chemical reaction or crosslinking between PAN and lignin in the solution. However, the resulting carbon fibers display a large I_D/I_G ratio (by Raman spectroscopy) indicating a larger disordered as compared to that from pure PAN. The macro‐voids in the lignin/PAN blend fibers typically generated during wet‐spinning were eliminated by adding lignin in the coagulant bath to counter‐balance the out‐diffusion of lignin. Carbon fibers resulting from lignin/PAN blends with 50 wt % lignin content displayed a tensile strength and modulus of 1.2 ± 0.1 and 130 ± 3 GPa, respectively, establishing that the equi‐component wet‐spun L/P‐based carbon fibers possessed tensile strength and modulus higher than 1 and 100 GPa. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45903.     

Chemorheology and thermomechanical characteristics of benzoxazine‐urethane copolymers

In this research, processability and some important thermomechanical properties of polybenzoxazine (BA‐a) modified with a highly flexible urethane elastomer (PU) are discussed. This copolymer has been reported to show synergy in its glass transition temperature and some mechanical properties thus provides a fascinating group of high temperature polymers with enhanced flexibility. The results reveal that a processing window of the BA‐a/PU mixtures is widened with the increasing urethane prepolymer fraction, that is, the liquefying temperature is lowered and the gel point shifted to higher temperature with the amount of the PU. Synergism in glass transition temperature (T_g) of this copolymer was clearly confirmed, i.e., T_g's of the BA‐a/PU alloys were significantly greater than those of the parent resins, i.e., BA‐a (T_g = 166°C) and PU (T_g = ? 70°C). In addition, flexural modulus was found to systemically decrease from 5.4 GPa of the neat polybenzoxazine to 2.1 GPa at 40% by weight of the PU. Flexural strength of the alloys also shows a synergistic behavior at the BA‐a/PU ratio of 90/10. Coefficient of thermal expansion of the polymer alloys were also found to show a minimum value at BA‐a/PU = 90/10. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dependence of the Mechanical Sensitivity on the Fractal Characteristics of Octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine Particles

Three fabrication methods were used to synthesize HMX powders with different particle sizes and microscopic morphologies. All as‐prepared samples were characterized by laser granularity measurements and scanning electron microscopy (SEM). The mechanical sensitivity and thermal stability of the different HMX powders were characterized using mechanical sensitivity tests and differential scanning calorimetry (DSC). Size distribution data and SEM images were used to find the size fractal dimension (D) and surface fractal dimension (D_s) of HMX samples, which were calculated by the least‐squares method and fractal image processing software (FIPS), respectively. The parameters D and D_s quantize two important properties of HMX particles, namely the complexity of the particle size distribution and the irregularity of the particle surface, which affect the thermal conductivity of the particle group if it is exposed to stimuli such as impact, friction or heating. The fractal dimensions reveal the dependence of the mechanical sensitivity of HMX on the powder size, size distribution and microscopic morphology. The results indicate that the proportion of fine particles in HMX powder increases as the D value increases, which causes decreased impact sensitivity. This occurs because hot spot formation leading to an explosion is more difficult because of the improved thermal conductivity of the particle group. Similarly, the surface roughness of HMX particles increases with an increase in D_s, causing an increase in friction sensitivity because of the excessive accumulation of frictional heat. In addition, thermal analysis results indicate that the maximum thermal decomposition rate of HMX decreases with increasing D and D_s.     

Structure–property relationship of starch‐filled chain‐extended polyurethanes

Chain‐extended polyurethane (PU) elastomers were prepared using castor oil with 4,4′‐methylene bis (phenyl isocyanate) (MDI) as a crosslinker and 4,4′‐diamino diphenyl sulphone (DDS) as an aromatic diamine chain extender. A series of starch‐filled (from 5 to 25% wt/wt) diamines chain‐extended PUs have been prepared. The starch‐filled PU composites were characterized for physico‐mechanical properties viz, density, surface hardness, tensile strength, and percentage elongation at break. Thermal stability of PU/starch have been carried out by using thermogravimetric analyzer (TGA). Thermal degradation process of PU/starch were found to proceed in three steps. TGA thermograms of PU/starch shows that all systems were stable upto 235°C, and maximum weight loss occur at temperature 558°C. The microcrystalline parameters such as crystal size (〈N〉) and lattice strain (g in %) of PU/starch have been established using wide‐angle X‐ray scattering (WAXS) method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2945–2954, 2003     

Synthesis of biodegradable polyurethanes chain‐extended with (2S)‐bis(2‐hydroxypropyl) 2‐aminopentane dioate

Polyurethanes (PUs) are the most widely used polymers because of their biocompatibility, tunable mechanical properties, and chemical versatility. In this study, a two‐step condensation polymerization of polycaprolactone diol and hexamethylene diisocyanate was carried out, and a glutamic acid ester derivative, (2S)‐bis(2‐hydroxypropyl) 2‐aminopentane dioate (HPAP), was used as a new chain extender to accelerate the biodegradation properties of PU. HPAP was synthesized by the Fischer esterification of l ‐glutamic acid. The chemical structure of HPAP was confirmed by high‐resolution mass spectroscopy and m/z (EI) was found to be 264.1447 [calculated value = 264.1443 for C₁₁H₂₁NO₆ (M⁺)]. The Berry plot of static light‐scattering measurements showed that PU–HPAP had a weight‐average molecular weight and radius of gyration of 33,100 g/mol and 1420 nm, respectively. The presence of HPAP in the PU structure facilitated hydrogen bonding between the polymer chains and increased the glass‐transition temperature from ?56 °C (PU) to ?50 °C (PU–HPAP). PU–HPAP showed the highest hydrophilicity and surface free energy among all of samples, and this accelerated the in vitro biodegradation period via surface erosion. In addition, PU–HPAP did not show any cytotoxic effects on the L929 cells. A new biodegradable and biocompatible PU–HPAP was obtained as candidate for tissue engineering applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45764.     

Fractal analysis of polypropylene composite filled with nano‐calcium carbonate

Polypropylene (PP) and nano‐calcium carbonate (CaCO₃) composites were prepared by melt mixing in a corotating twin‐screw extruder. Transmission electron microscopy study and particle size analysis revealed the dispersion and the size distribution of CaCO₃ in PP. With the increase of loading of filler, CaCO₃ nanoparticles densely aggregated together and the dispersion of filler became bad. The fractal dimensions of the composites were determined using fractal concept. The fractal dimensions of D and D_k described the irregularities of the shape of an object and the distributions of particle populations, respectively. The D and D_k values were influenced by the content of filler, i.e., the D values increased, and the D_k values decreased with the increase of loading of filler. When the loading of filler was low, the values of D and D_k of PP composites differ slightly than the counterparts of PP/PP‐g‐MA (50 wt %) blend. For 20 wt %, they were almost identical. This fact showed that the fractal dimension was correlated with the dispersion. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Transport characteristics of carboxylic acids based chain extended PU membranes with n‐alkane penetrants

Castor oil based chain extended polyurethanes (PUs) have been prepared using citric acid and maleic acid as chain extenders. Molecular transport of n‐alkanes into prepared carboxylic acid chain extended PUs has been studied at different temperatures, viz., 25, 40, and 60°C using a gravimetric sorption method. The sorption (S), the diffusion (D), and the permeation (P) coefficients for n‐alkane penetrants have been calculated. Transport data are affected by the nature of the interacting solvent molecules, molar volume, solubility parameters, temperature, and the structural variation of the chain extended PUs. The temperature dependence of the transport coefficient has been used to estimate the kinetic parameters for the processes of diffusion (E_D) and permeation (E_P) from the Arrhenius plots. The van't Hoff relation was used to obtain enthalpy (ΔH) and entropy (ΔS) of sorption process. POLYM. ENG. SCI., 47:2057–2064, 2007. © 2007 Society of Plastics Engineers     

Spin probe study of semi‐interpenetrating polymer networks based on polyurethane and polymethacrylate functional prepolymers

The motional transition and heterogeneity of semi‐interpenetrating networks (SIPNs) based on polyurethane (PU) with carboxylic groups and methacrylic copolymer (PM) with tertiary amine groups were studied by the electron spin resonance (ESR) spin probe method. The concentration of functional groups in both prepolymers varied from 0 to 0.45 mmol g^?1. Spin‐probed SIPNs show that the temperature‐dependent spectra are sensitive to polymer interactions imposed by functional groups. These interactions determine the free volume distribution in the matrix and temperature at which motional transition takes place. The fraction of free volume increases with functional group concentration and reaches its maximum at 0.25 mmol g^?1. Further increases in the functional group concentration reduce the free volume. The results of the networks with strong interactions are discussed in terms of the interference of the plasticizing effect of the PU component and the formation of possible cluster cross‐links, which restricts segmental motions. Copyright © 2003 Society of Chemical Industry