Uralkyd and poly (butyl methacrylate) interpenetrating polymer networks

ABSTRACT:: Hydroxyl terminated alkyds synthesized from castor oil, glycerol, and different dibasic acids were used to develop uralkyds and their interpenetrating polymer networks (IPNs) with polybutyl methacrylate (PBMA). Glass transition temperature measurements gave the evidence of interpenetration. The IPNs were characterized for their physicomechanical properties and their phase morphology was studied by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). As the concentration of the uralkyd in IPNs increases, a gradual increase in elongation, density, and swelling with a consequent decrease in the hardness were observed for all IPNs. Swelling is relatively more prominent in methyl ethyl ketone (MEK) and toluene than in water. From SEM it was observed that IPNs of PBMA‐uralkyd containing phthalic anhydride (UA‐P) as an acid part showed greater compatibility than those containing dimethyl terephthalate (UA‐D). From thermogravimetric analysis (TGA) no significant change was observed in the degradation behavior of the IPNs. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 825–832, 2000     

New interpenetrating polymer networks based on uralkyd–poly(butyl methacrylate)

A study on two‐component semi‐ and full‐interpenetrating polymer networks (IPNs) of soyabean‐oil based uralkyd resin (UA) and poly(butyl methacrylate) (PBMA) synthesized by a sequential technique, has been conducted. The IPNs obtained are characterized with respect to their mechanical properties, such as tensile strength, percentage elongation and hardness (Shore A). Phase morphology has been studied by scanning electron microscopy. Glass transition studies have been carried out using differential scanning calorimetry. The thermal characterization of the IPNs was undertaken with the aid of thermogravimetric analysis. The apparent densities of these samples have been determined and are compared. The effect of the compositional variation on the above‐mentioned properties was examined. The tensile strength exhibits a sudden rise (approximately three‐fold) for the semi‐ and full‐IPNs with composition UA: PBMA 40% : 60% compared with the UA:PBMA composition of 20% : 40%. © 2001 Society of Chemical Industry     

聚氨酯/聚甲基丙烯酸甲酯互穿网络的阻尼性能及相态

引言聚合物互穿网络体系由于在其形成过程中产生特殊的物理拓扑结构,使得该体系是一种永久缠结在一起的聚合物"合金"[1]。同时,由于构成该体系的聚合物组分往往不相容或部分相容,在其形成     

Second order non-linear optical interpenetrating polymer networks based on polyurethane or poly(methyl methacrylate) and epoxy polymer

Two interpenetrating polymer networks (IPNs), (one pseudo-IPN consisting of a linear polyurethane/epoxy-based polymer network and one full-IPN consisting of a poly(methyl methacrylate)/epoxy-based polymer network) have been synthesized and characterized. Both IPNs showed only one T_g; hence a homogeneous phase morphology is suggested. The second-order non-linear optical coefficients (d₃₃) of the pseudo-IPN and the full-IPN were measured and found to be 2.78 × 10⁻⁷ esu and 1.86 × 10⁷ esu, respectively. The study of temporal stability at room temperature and elevated temperature (120 °C) indicates that the full-IPN is more efficient at improving the orientational stability of the non-linear optical chromophores than the pseudo-IPN, because of the permanent entanglements of the two component networks in the full-IPN. © 1999 Society of Chemical Industry     

Main chain and segmental dynamics of semi interpenetrating polymer networks based on polyisoprene and poly(methyl methacrylate)

Main chain and segmental dynamics of polyisoprene (PI) and poly(methyl methacrylate) (PMMA) chains in semi IPNs were systematically studied over a wide range of temperatures (above and below T_g of both polymers) as a function of composition, crosslink density, and molecular weight. The immiscible polymers retained most of its characteristic molecular motion; however, the semi IPN synthesis resulted in dramatic changes in the motional behavior of both polymers due to the molecular level interpenetration between two polymer chains. ESR spin probe method was found to be sensitive to the concentration changes of PMMA in semi IPNs. Low temperature spectra showed the characteristics of rigid limit spectra, and in the range of 293-373 K, complex spectra were obtained with the slow component mostly arising out of the PMMA rich regions and fast component from the PI phase. We found that the rigid PMMA chains closely interpenetrated into the highly mobile PI network imparts motional restriction in nearby PI chains, and the highly mobile PI chains induce some degree of flexibility in highly rigid PMMA chains. Molecular level interchain mixing was found to be more efficient at a PMMA concentration of 35 wt.%. Moreover, the strong interphase formed in the above mentioned semi IPN contributed to the large slow component in the ESR spectra at higher temperature. The shape of the spectra along with the data obtained from the simulations of spectra was correlated to the morphology of the semi IPNs. The correlation time measurement detected the motional region associated with the glass transition of PI and PMMA, and these regions were found to follow the same pattern of shifts in α-relaxation of PI and PMMA observed in DMA analysis. Activation energies associated with the T_g regions were also calculated. T_50G was found to correlate with the T_g of PMMA, and the volume of polymer segments undergoing glass transitional motion was calculated to be 1.7 nm³. C-13 T_1ρ measurements of PMMA carbons indicate that the molecular level interactions were strong in semi IPN irrespective of the immiscible nature of polymers. The motional characteristics of H atoms attached to carbon atoms in both polymers were analyzed using 2D WISE NMR. Main relaxations of both components shifted inward, and both SEM and TEM analysis showed the development of a nanometer - sized morphology in the case of highly crosslinked semi IPN.     

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     

High-resolution thermogravimetric analysis of polyurethane/poly(ethyl methacrylate) interpenetrating polymer networks

Thermal degradation of a series of polyurethane/poly(ethyl methacrylate) interpenetrating polymer networks and their constituent networks were studied by three modes of thermogravimetric analysis: the conventional method, the constant reaction rate method, and the dynamic rate technique. The best understanding of the degradation mechanism was achieved by the last method, which allows much better resolution of overlapping events. In addition, the weight losses correspond well with the results obtained from the constant reaction rate analysis, but are achieved in shorter times. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 287–295, 1998     

Semi‐ and full‐interpenetrating polymer networks based on polyurethane produced from canola oil and poly(methyl methacrylate)

Semi‐ and full‐interpenetrating polymer networks (IPNs) were prepared using polyurethane (PUR) produced from a canola oil‐based polyol with primary terminal functional groups and poly(methyl methacrylate) (PMMA). The properties of the material were studied and compared using dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and tensile measurements. The morphology of the IPNs was investigated using atomic force microscopy (AFM). Semi‐IPNs demonstrated different thermal mechanical properties, mechanical properties, phase behavior, and morphology from full IPNs. Both types of IPNs studied are two‐phase systems with incomplete phase separation. However, the extent of phase separation is significantly more advanced in the semi‐IPNs compared with the full IPNs. All the semi‐IPNs exhibited higher values of elongation at break for all proportions of acrylate to polyurethane compared with the corresponding full IPNs. These differences are mainly due to the fact that in the case of semi‐IPNs, one of the constituting polymers remains linear, so that it exhibits a loosely packed network and relatively high mobility, whereas in the case of full IPNs, there is a higher degree of crosslinking, which restricts the mobility of the chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Epoxy resin–poly(ethyl methacrylate) interpenetrating polymer networks: Morphology,mechanical, and thermal properties

Full (interpenetrating networks (IPNs)) and semi-IPNs of the epoxy resin and poly(ethyl methacrylate) (PEMA) were prepared by the sequential mode of synthesis. These were characterized with respect to their mechanical properties, namely, tensile strength, elongation at break, modulus, and toughness. Thermal properties were studied by differential scanning calorimetry and thermogravimetry. The morphological features were studied through scanning electron microscopy (SEM) and polarized light microscopy. The effects of variation of the blend ratios on the above-mentioned properties were examined. There was a gradual decrease of modulus and tensile strength with consequent increases in elongation at break and toughness for both types of IPNs with increases in PEMA content. The weight retentions in the thermal decomposition of both the semi-IPNs and full IPNs were higher than the epoxy homopolymer. This enhancement was presumably related to the presence of the unzipped ethyl methacrylate monomer, which acted as radical scavengers in the epoxy degradation. An inward shift and lowering (with respect to pure epoxy) of the T_g of the IPNs was observed. The polarized light microscopy exhibits bimodal distribution of particle sizes. The fractography as studied by SEM shows change in fracture mechanics from shear yielding to crazing with increasing PEMA content. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1051–1059, 1998     

Miscibility and thermal and dynamic mechanical behaviour of semi‐interpenetrating polymer networks based on polyurethane and poly(hydroxyethyl methacrylate)

The thermodynamic miscibility and thermal and dynamic mechanical behaviour of semi‐interpenetrating polymer networks (semi‐IPNs) of crosslinked polyurethane (PU) and linear poly(hydroxyethyl methacrylate) (PHEMA) have been investigated. The free energies of mixing of the semi‐IPN components have been determined by the vapour sorption method and it was established that the parameters are positive and depend on the amount of PHEMA in the semi‐IPN samples. Thermal analyses glass transition temperatures evidenced two in the semi‐IPNs in accordance with the investigation of the thermodynamic miscibility of these systems. Dynamic mechanical analysis revealed a pronounced change in the viscoelastic properties of the PU‐based semi‐IPNs with different amounts of PHEMA in the samples. The semi‐IPNs have two distinct tan δ maxima related to the relaxations of the two polymers in their glass temperature domains. The temperature position of PU relaxation maximum tan δ is invariable but its amplitude decreases in the semi‐IPNs with increasing amount of PHEMA in the systems. The tan δ maximum of PHEMA is shifted to a lower temperature and its amplitude decreases with increasing amount of PU in the semi‐IPNs. The segregation degree of components α was calculated using the viscoelastic properties of semi‐IPNs. It was concluded that the studied semi‐IPNs are two‐phase systems with incomplete phase separation. The different levels of immiscibility lead to the different degree of phase separation in the semi‐IPNs with compositions. Copyright © 2004 Society of Chemical Industry     

Polyurethane-polysiloxane interpenetrating polymer networks: 1. A polyether urethane-poly(dimethylsiloxane) system

The synthesis and properties of a polyether urethane network based on Adiprene L-100, of a poly(dimethylsiloxane) network and of nine interpenetrating polymer networks based on these polymers were investigated. To form the latter materials, the prepolymers were mixed and crosslinked simultaneously, but by separate mechanisms. Comparison of the network solubility parameters suggested marked incompatibility. Optical microscopy, dynamic mechanical analysis and the tensile testing indicated gross phase separation. From 90 to 50% of the polyether urethane component, this network was continuous and the poly(dimethylsiloxane) was present as dispersed phases. From 40 to 10% of the polyether urethane, the situation was reversed. Some degree of interchain mixing at phase boundaries was detected by ¹³C nuclear magnetic resonance spectroscopy.     

Synthesis and characterization of sequential interpenetrating polymer networks of novolac resin and poly(ethyl acrylate)

Interpenetrating polymer networks (IPN) of Novolac/poly(ethyl acrylate) have been prepared via in situ sequential technique of IPN formation. Both full and semi IPNs were characterized with respect to their mechanical properties that is, ultimate tensile strength (UTS), percentage elongation at break, modulus, and toughness. Physical properties of these were evaluated in terms of hardness, specific gravity, and crosslink density. Thermal behavior was studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The morphological features were observed by an optical microscope. There was a gradual decrease in modulus and UTS, with consequent increases in elongation at break and toughness for both types of IPNs with increasing proportions of PEA. An inward shift and lowering (with respect to pure phenolic resin) of the glass transition temperatures of the IPNs with increasing proportions of PEA were observed, thus, indicating a plasticizing influence of PEA on the rigid, brittle, and hard matrix of crosslinked phenolic resin. The TGA thermograms exhibit two‐step degradation patterns. An apparent increase in thermal stability at the initial stages, particularly, at lower temperature regions, was followed by a substantial decrease in thermal stability at the higher temperature region under study. As expected, a gradual decrease in specific gravity and hardness values was observed with increase in PEA incorporation in the IPNs. A steady decrease in crosslink densities with increase in PEA incorporation was quite evident. The surface morphology as revealed by optical microscope clearly indicates two‐phase structures in all the full and semi IPNs, irrespective of acrylic content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

SBS/P(St-MMA)热塑性互穿聚合物网络结构与力学性能

采用原子转移自由基聚合(ATRP)法合成了苯乙烯一甲基丙烯酸甲酯共聚物[P(St-MMA)]。采用分步法制备了SBS／P(St-MMA)热塑性互穿聚合物网络(TIPN)。研究了P(St-MMA)质量分数、MMA／St(摩尔比,下同)和不同聚合方式对TIPN结构和力学性能的影响。结果表明：生成了具有较窄相对分子质量分布的P(St-MMA);P(St-MMA)质量分数在30％,左右时,采用ATRP法制备的SBS／P(St-MMA)TIPN拉伸强度和扯断伸长率达到最大;随MMA／St增加,TIPN拉伸强度增大,扯断伸长率不变。常规自由基聚合法制备的TIPN与ATRP法相比,前者相对分子质量高,相对分子质量分布宽,拉伸强度高,扯断伸长率随P(St-MMA)质量分数增加而下降。     

Transition behaviour of polyurethane-poly(methyl methacrylate) interpenetrating polymer networks

The transition behaviour of polyurethane-poly(methyl methacrylate) interpenetrating polymer networks (PUR/PAc IPN's) was studied by means of differential scanning calorimetry (d.s.c.), dynamic mechanical spectroscopy (d.m.s.) and thermally stimulated depolarization (t.s.d.). Instead of a sharp discontinuity in heat capacity, as for the individual networks, a very broad change is observed by calorimetry and some intermediate changes in heat capacity appear too. D.m.s. yields only two peaks which show a marked inward shift, with an important damping and broadening, as compared to the individual networks. Some preliminary results obtained by t.s.d. confirm these findings. It can be concluded that PUR/PAc IPN's are phase separated, but that the mutual miscibility of both components is enhanced by the special mode of combining them, namely interpenetration. When the second component is not crosslinked, phases appear to be less entangled. Previous results on physical and mechanical properties corroborate these conclusions.     

Synthesis and properties of elastomer‐modified epoxy–methacrylate sequential interpenetrating networks

The structure and properties of copolymerized sequential‐interpenetrating networks (SeqIPNs) synthesized from amine‐cured epoxies and free‐radical polymerized dimethacrylates were examined. Materials were synthesized with and without the incorporation of an epoxy‐terminated butadiene–nitrile reactive elastomer. Synthesis proceeded through full thermal cure of the epoxy–amine network, followed by polymerization of the methacrylate network. The methacrylate reactions were free‐radically induced using thermal (peroxide‐initiated) or photochemical [electron‐beam (e‐beam)] techniques. Fourier transform infrared spectroscopy was used to monitor epoxy–amine step‐growth polymerization in situ and to measure final cure conversion of methacrylates. Structural examination of the IPNs using atomic force microscopy and scanning electron microscopy revealed microphase separation in the neat–SeqIPN materials and macroscopic phase separation of rubber‐rich domains for elastomer‐modified networks. Dynamic mechanical analysis of the SeqIPN determined that the properties of the network are strongly dependent on the cure conditions. Furthermore, the viscoelastic behavior of the e‐beam–cured SeqIPN could be adequately described by the Williams–Landel–Ferry and Kohrausch–Willams–Watts equations, presumably because of a strong coupling between the epoxy–amine and methacrylate networks. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 530–545, 2001     

Synthesis and characterization of polyurethane/poly(vinylidene chloride) interpenetrating polymer networks

A series of polyurethane (PU)/poly(vinylidene chloride) (PVDC) interpenetrating polymer networks (IPNs) were synthesized through variations in the amounts of the prepolyurethane and vinylidene chloride monomer via sequential polymerization (80/20, 60/40, 50/50, 40/60, 30/70, and 20/80 PU/PVDC). The physicomechanical and optical properties of the IPNs were investigated. Thermogravimetric analysis (TGA) studies of the IPNs were performed to establish their thermal stability. TGA thermograms showed that the thermal degradation of the IPNs proceeded in three steps. Microcrystalline parameters, such as the crystal size and lattice disorder, of the PU/PVDC IPNs were estimated with wide‐angle X‐ray scattering. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1375–1381, 2007     

Fabrication and apparent kinetic study of poly(methyl methacrylate)/poly(octyl acrylate) and poly(octyl acrylate)/poly(methyl methacrylate) latex interpenetrating polymer networks

Two latex interpenetrating polymer networks (LIPNs) were synthesized with methyl methacrylate (MMA) and octyl acrylate (OA) as monomers, respectively. The apparent kinetics of polymerization for the LIPNs was studied. This demonstrates that network II does not have a nucleus formation stage. The monomers of network II were diffused into the latex particles of network I and then formed network II by in situ polymerization. It indicates that the polymerization of network I obeys the classical kinetic rules of emulsion polymerization. But the polymerization of network II only appears a constant‐rate stage and a decreasing‐rate stage. The apparent activation energies (E_a) of network I and network II of PMMA/POA were calculated according to the Arrhenius equation. The E_a values of POA as network I (62 kJ/mol) is similar to that of POA as network II PMMA/POA (60 kJ/mol). However, the E_a value of PMMA as network II POA/PMMA (105kJ/mol) is higher than that of PMMA as network I (61 kJ/mol). Results show that the E_a value of the network II polymerization is related to the properties of its seed latex. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterizations of interpenetrating polymer network hydrogels of poly(ethylene oxide) and poly(methyl methacrylate)

Interpenetrating polymer network (IPN) hydrogels based on poly(ethylene oxide) and poly(methyl methacrylate) were prepared by radical polymerization using 2,2‐dimethyl‐2‐phenylacetophenone and ethylene glycol dimethacrylate as initiators and crosslinkers, respectively. The IPN hydrogels were analyzed for sorption behavior at 25°C and at a relative humidity of 95% using dynamic vapor sorption. The IPN hydrogels exhibited a relatively high equilibrium water content in the range of 13–68%. The state of water in the swollen IPN hydrogels was investigated using differential scanning calorimetry. The free water in the hydrogels increased as the hydrophilic content increased. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 258–262, 2003     

Preparation of SBS/poly(styrene–methyl methacrylate) thermoplastic interpenetrating polymer network

SBS as polymer I, poly(styrene–methyl methacrylate) polymerized by atom transfer radical polymerization as polymer II, and a thermoplastic interpenetrating polymer network of SBS/poly(styrene–methyl methacrylate) were prepared by the sequential method. The effects of the polymerization temperature, the composition of the catalyst, the ratio of the monomers studied, and the kinetics at 90°C were also investigated. It was shown that when polymerization was initiated by a BPO/CuCl/bpy (BPO:CuCl:bpy = 1:1:3) system at 90°C, the mass averaged molecular weight of the poly(styrene–methyl methacrylate) increased with monomer conversion, and the polydispersities were kept very low. Fourier transform infrared spectroscopy and gel permeation chromatogram showed that poly(styrene–methyl methacrylate) with low polydispersities had been synthesized. Thus, a thermoplastic interpenetrating polymer network comprised of both narrow molecular‐weight‐distribution components was successfully prepared. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2007–2011, 2003     

Sequential interpenetrating polymer networks of novolac resin and poly(n‐butyl methacrylate)

Novolac resin/poly(n‐butyl methacrylate), P(n‐BMA), sequential interpenetrating polymer networks (both semi and full types) were prepared and characterization of the various compositions (up to 40% by weight of PF incorporation) was performed in terms of mechanicals, namely, ultimate tensile strength (UTS), percentage elongation at break (% E.B.), modulus, and toughness. Thermal properties were studied by differential scanning calorimetry and thermogravimetric analysis (TGA). Crosslink densities of the IPNs were calculated using Flory‐Rehner equation. The morphological features were studied through scanning electron microscope. There was a gradual decrease of modulus and UTS with consequent increases in % E. B. and toughness with increasing proportions of P(n‐BMA). An inward shifting and lowering of the glass transition temperatures of the IPNs (compared with that of pure phenolic resin) with increasing proportions of P(n‐BMA) were observed. The TGA thermograms exhibit two‐step degradation patterns. A typical cocontinuous bi‐phasic morphology is evident in the micrographs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4030–4039, 2006