Semi- and fully interpenetrating polymer networks based on polyurethane-polyacrylate systems. X. Polyurethane-poly(ethyl acrylate) interpenetrating polymer networks

A series of polyurethane-poly(ethyl acrylate) interpenetrating networks (IPNs) containing 40 wt% polyurethane were prepared, in which the cross-link density of the polyurethane component was varied by altering the ratio of diol/triol. Decreasing the molecular weight between crosslinks from 9500 to 1200 g/mol brought about an increase in the tensile strength accompanied by a decrease in elongation at break. The tensile properties of the IPNs are, however, poorer than those of the equivalent polyurethane homopolymers. Electron microscopy showed that the polyurethane was present as distinct phases, connected by a cellular fine structure, in the poly(ethyl acrylate) matrix. Dynamic mechanical analysis as well as sonic velocity studies gave results which were consistent with this morphological picture.     

Polysiloxane-poly(fluorinated acrylate) interpenetrating polymer networks: Synthesis and characterization

Combinations of fluorinated and silicone based elastomers were elaborated through the in situ synthesis of interpenetrating polymer networks (IPNs). The PDMS network was formed by dibutyltindilaurate catalyzed addition between the hydroxy end groups of α,ω-(3-hydroxypropyl)polydimethylsiloxane (PDMS) and a pluriisocyanate cross-linker. The poly(fluorinated acrylate) (polyAcRf6) network was obtained from free-radical copolymerization of a fluorinated acrylate with ethylene glycol dimethacrylate in the presence of dicyclohexyl peroxydicarbonate as the initiator. IPNs with different relative weight proportions of the fluorinated vs silicone partners were characterized by DMTA and DSC. Density refractive index and contact angle measurements reveal a satisfactory interpenetration degree of PDMS and polyAcRf6 networks. In addition, these materials present an unusual variation of density values and of the surface properties as a function of the relative weight composition.     

Synthesis and characterization of sequential interpenetrating polymer networks of polyurethane acrylate and polybenzoxazine

High‐performance ultraviolet (UV) curable polyurethane acrylate (PUA) coating alloyed with thermally curable polybenzoxazine (PBA) is developed. The hybrid polymer networks of PUA and PBA‐a were prepared by sequential cure methods, i.e., UV cure of the PUA followed by thermal cure of the PBA fraction. The effects of sequential cure were investigated in terms of mechanical, thermal, and physical properties of the resulting polymer alloys. The fully cured PUA/PBA‐a alloy films showed only single glass transition temperature (T_g) suggesting high compatibility between the two polymer networks, possibly of an interpenetrating polymer network type. The storage modulus in a glassy state and T_g of PUA/PBA‐a alloys were found to substantially increase with increasing PBA‐a content. Furthermore, degradation temperature at 10% weight loss of the PUA/PBA‐a alloy films was relatively high whereas the char yield at 800°C was found to increase with a PBA‐a component. Hardness was enhanced, whereas water absorption and water vapor permeation rate of the alloy were suppressed by the incorporation of the PBA‐a into the polymer alloys. As a consequence, the properties of UV curable PUA networks can be positively tailored and enhanced by forming hybrid network with PBA‐a. POLYM. ENG. SCI., 54:1151–1161, 2014. © 2013 Society of Plastics Engineers     

Controlling properties of acrylate/epoxy interpenetrating polymer networks by premature termination of radical polymerization of acrylate

An approach is presented to control properties of sequentially synthesized acrylate/epoxy interpenetrating polymer networks (IPNs) and is used to print uniform and graded properties. These IPNs are constructed by partial formation of the acrylate network, removal of the excess components, expansion with the epoxy system, and curing. The partial crosslinking of the initial network is controlled by photo polymerization and used to manipulate the final properties. The process is used to print homogeneous and graded IPNs with properties in the range of 10 to 1000 MPa. The curing of acrylate, the control mechanism, is studied by Fourier Transform Infrared Spectroscopy (FTIR) during curing on a temperature and environment controlled attenuated total reflection system. Fast scanning calorimetry is used to study network formation, nanoindentation is used to characterize local change of modulus, and uniaxial tensile testing is used to characterize stress response of the printed systems. POLYM. ENG. SCI., 59:1729–1738 2019. © 2019 Society of Plastics Engineers     

聚丙烯酸乙酯/聚异冰片酯镶嵌型乳液互穿聚合物网络

用多步种子乳液聚合法合成了微交联结构的复合乳液聚丙烯酸乙酯(xPEA)／聚异冰片酯(xPIBA)。利用异冰片酯超大的侧基得到具有很高Tg的聚合物的复合物。TEM照片显示，这种乳液具有镶嵌式的结构，DSC分析表明，2种聚合物之间是互穿聚合物网络的关系。当xPEA／xPIBA的质量比为75／25，其中二者TEGDA质量分数分别为0．5％和0．15％时，塑性加工后，试样拉伸强度可达6．8MPa，扯断伸长率为412％，永久变形小于50％。试样在120℃仍然保持3.5MPa的拉伸强度。     

Elastomeric domain-type interpenetrating polymer networks

Elastomeric latex interpenetrating polymer networks (IPNs) can result from a two-stage emulsion polymerization procedure in which styrene is polymerized and cross-linked on a lightly cross-linked polyacrylate (PA) seed latex in a ratio of 75 : 25 PA-PS. The multiphase nature of these IPNs is indicated by two distinct T_gs and is confirmed by cold-stage transmission electron microscopy and by the unique mechanical and rheological properties that are intimately related to the material's structure. PS microdomains reinforce the elastomeric PA, yielding a significant modulus, and interparticle PS physical ties yield a significant ultimate tensile strength. The elastomeric latex IPN's dual thermoset-thermoplastic nature is revealed in a stick, slip, roll flow mechanism of the cross-linked submicrometer particles, which can be injection molded as a thermoplastic. The relationships among the polymerization procedure, the structure, and the physical properties are characterized by the examination of several different materials using a variety of analytic techniques.     

Semi- and fully interpenetrating polymer networks based on polyurethane–polyacrylate systems. VII. Polyurethane–poly(methyl acrylate) interpenetrating polymer networks

A series of polyurethane–poly(methyl acrylate) sequential interpenetrating polymer networks containing 40 wt % polyurethane were prepared. The triol/diol ratio used in the preparation of the first formed polyurethane network was changed so that the average molecular weight between crosslinks ranged from 9500 to 500 g/mol. In addition to decreasing this average molecular weight, changing the triol/diol ratio alters the hard segment content of the polyurethane. The extent of mixing of the components in these IPNs was investigated using electron microscopy, dynamic mechanical analysis, tensile testing, and sonic velocity measurements. The polyurethane networks were also characterized by swelling studies. It was concluded that, as the triol/diol ratio increased, the extent of mixing increased and there was evidence of phase separation of the hard segments of the polyurethane component at high triol/diol ratios.     

Recent advances in interpenetrating polymer networks

Interpenetrating polymer networks (IPN's) can be defined as a combination of two polymers in network form, at least one of which was synthesized and/or crosslinked in the immediate presence of the other. Historically, the science of IPN's began with the papers of J. R. Millar in 1960 on homo-IPN's made from polystyrene, but the first recorded publication is a patent by J. W. Aylsworth in 1914. This latter system was based on phenol-formaldehyde for one network, and sulfur cured natural rubber for the other network. Early academic laboratories interested in IPN's include the Frisch team at Detroit and SUNY, who soon added their former student, Danny Klempner, and Yuri Lipatov's team at the Ukranian SSR Academy of Sciences in the USSR, as well as the author's laboratory. More recent academic teams interested in IPN's include Douglas Hourston at the University of Lancaster, England; Robert Cohen at MIT; S. C. Kim at the Korea Advanced Institute of Science and Technology, Seoul, Korea; G. Meyer and J. M. Widmaier in Strasbourg, France; and many others. Numerous industrial laboratories are interested, noting that about 90 U.S. patients have been granted, most of them in the past ten years. Systems of special interest include the new thermoplastic IPN's, which are really hybrid materials between polymer blends and IPN's, and the IPN-based RIM (reaction injection molding) materials. Other materials include the sequential IPN's and the SIN's, which have both polymers simultaneously polymerized, and the latex IPN's, which often exhibit core-shell characteristics.     

Recent studies on interpenetrating polymer networks

Recent investigations on interpenetrating polymer networks (IPNs) have included two component IPNs from polyurethanes and poly(methacrylates) and two component IPNs from polyurethanes and epoxies. All the IPNs were prepared by the simultaneous polymerization technique (SIN-IPNs). Two types of IPNs, polyurethane-poly(methyl methacrylate) (PU/PMMA) and polyurethane-poly(methyl methacrylate-methacrylic acid) (PU/PMMA-MAA) were prepared. Improved phase miscibility and decreasing extent of phase separation was observed in both types of IPNs with increasing the NCO/OH ratio, decreasing molecular weight of the polyol in the PU and introduction of charge groups. A comparison was made between full-IPNs, pseudo-IPNs, graft copolymers and related homopolymers from polyurethanes and epoxies. Increased compatibility in full-IPNs and graft copolymers was observed by means of DSC, SEM and was also further substantiated by a shift toward single T_gs as determined by dynamic mechanical spectroscopy. The introduction of opposite charge groups in two-component IPNs from polyurethanes and epoxies led to improved compatibility (no phase separation) and enhanced mechanical properties.     

Thermodynamic characterization of interpenetrating polymer networks

Crosslinked poly(methyl methacrylate) (PMMA-c), poly(carbonate-urethane) (PCU-c), poly(vinyl pyridine) (PVP-c), and full, simultaneous interpenetrating polymer networks (IPNs) based on the above polymers were characterized by precise heat capacity (C_p) measurements in the temperature interval 4.2–450 K. The raw values of C_p scaled with temperature (T) as C_p ∼ T^d with d = 2 and 5/3, as expected for a fracton-like vibration regime, in the temperature intervals 8–10 and 10–30 K, respectively. A single glass transition temperature (T_g) and two T_g's were observed for apparently homogeneous and microphase-separated IPNs, respectively. Judged by the positive sign of the excess Gibbs free energy, the apparently single-phase state of homogeneous IPNs is thermodynamically unstable; however, its kinetic stability is ensured by permanent topological constraints (network junctions) prohibiting the incipient phase separation.     

Recent advances in interpenetrating polymer networks

We review the synthesis, morphology, and physical and mechanical properties of IFNs as well as the related pseudo-IPNs, in which only one of the polymers is crossliriked. Recent studies have shown that the degree of phase separation achieved in these materials is strongly dependent on the compatibility of blends of the linear polymer constituents of the IPN components as well as the kinetics of chain extension and the presence of grafting between component polymers. We illustrate this by a series of IPNs consisting of a polyurethane and an acrylic copolymer. The acrylic is a typical automotive enamel. An enhancement in properties results, which is dependent on the amount of grafting and the kinetics of polymerization. Also discussed are IPNs of a polyurethane and an epoxy, which exhibit a synergism in adhesive properties, and IPNs of a RIM polyurethane with several epoxies and unsaturated polyesters. In addition, also reported are the preliminary studies on the first successful preparation of a three-component IPN, consisting of a polyurethane, an epoxy, and an acrylic.     

Polybutadiene/polystyrene interpenetrating polymer networks

Interpenetrating polymer networks (IPN's) of polybutadiene (PB) and polystyrene (PS) were prepared using both random (containing 36% cis, 55% trans, and 9% 1,2 vinyl) PB and high-cis PB. For both series, a wide range of PB/PS compositions were synthesized. Using samples stained with osmium tetroxide, electron microscope studies revealed an irregular cellular structure of a few hundred Ångstrom diameter with the first component, PB, making up the cell walls. The size of the cells was found to depend on the PB crosslink density for the random materials. Modulus-temperature data revealed two distinct glass transitions, confirming the microscopy finding of two phases. However, the transition temperature and transition slope varied with composition, and with the microstructure of the polybutadiene, giving evidence of significant molecular mixing. Stress-strain data on the IPN's showed that materials rich in PB behave like self-reinforced elastomers. Charpy impact resistance experiments on materials rich in PS indicated values of 5 ft-lb/in. of notch, which compares well with graft-type polyblends of similar PB/PS composition. The results were interpreted in the light of the recent theoretical work of Bragaw, who considered the importance of the distances between domain boundaries with respect to crack acceleration mechanics. Although the IPN's considered herein exhibited somewhat less than the predicted optimum phase dimensions, the arrangement of the domains is different from ordinary impact resistant plastics.     

丙烯酸丁酯/VAE互穿聚合物乳液的研究

以互穿聚合物网络(IPN)方法合成丙烯酸丁酯与VAE共聚物乳液。研究了乳化剂、交联剂、溶胀时间、反应时间等条件对转化率的影响。以红外光谱、透射电子显微镜表征互穿共聚物乳胶膜的微观结构。通过吸水性及乳胶膜对水接触角的测定，证明其耐水性较VAE乳胶膜明显增强。。YEM照片表明互穿聚合物胶粒形态结构较VAE乳胶粒发生了明显变化。     

Semi-1 thermoplastic interpenetrating polymer networks of physically crosslinked poly(n-butyl acrylate) and polystyrene

Poly(n-butyl acrylate) (PnBA) chemically crosslinked with tetraethylene glycol dimethacrylate (TEGDM) and physically crosslinked PnBAs produced by neutralization of poly(n-butyl acrylate-stat-acrylic acid) with NaOH or Ca(OH)₂ were prepared as a polymer I network. Each polymer I was swollen with styrene and cured in situ into semi-IPN-TEGDM, semi-IPN-Na, or semi-IPN-Ca, respectively. Both physically crosslinked polymers maintained their shapes during the swelling procedure. Dynamic mechanical spectroscopy indicated that good mixing of the two polymers took place in the semi-IPN-Ca as well as in semi-IPN-TEGDM, but a distinct phase separation occurred in the semi-IPN-Na. These results were supported by their transparent or optical opaque appearances, respectively. Annealing at 180°C developed further phase separation in the semi-IPN-Na, but very little in the semi-IPN-Ca. Analyses by the incompatibility number (based on the modulus–temperature curve) and the calculation of individual phase compositions (from the glass transition temperature shifts) were used in estimating the extent of molecular mixing.     

Vernonia oil–based acrylate and methacrylate polymers and interpenetrating polymer networks with epoxy resins

Acrylate and methacrylate monomers were obtained by reacting vernonia oil, a naturally epoxidized oil, with acrylic or methacrylic acid. The highest conversion (85–98%) of epoxy groups was obtained when the reaction was performed with an excess of the carboxylic acid at 100–120°C. The acrylate and methacrylate monomers of vernonia oil were characterized by IR and NMR spectroscopy. These monomers were then cured by sunlight in the presence of benzophenone to produce transparent films. In addition, interpenetrating polymer neworks (IPNs) were prepared in a two‐step technique from the sunlight‐cured methacrylate of vernonia oil, as the elastomeric component, in combination with a cured epoxy resin (a bisphenol A–type resin). Dynamic mechanical analysis showed good compatibility between the networks of the two cured polymers. An IPN with a 1 : 1 composition of the two polymer components exhibited the properties of a reinforced elastomer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3835–3843, 2004     

Synthesis and characterization of acrylate–oxetane interpenetrating polymer networks through a thermal-UV dual cure process

In the present work, a thermal-UV dual-cure process was performed on acrylate–oxetane systems. A 1:1 molar mixture of difunctional acrylate–oxetane mixture was prepared starting from 2,2-Bis(4-(3-acryloxy-2-hydroxypropoxy)phenyl)propane (BPADA) and 3-ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (OXT-221, DOX). Following a difunctional oxetane-acrylic monomer (OXAC) was synthesized.     

Structure-Property-Processing relationships of polyurethane-polyester interpenetrating polymer networks

Interpenetrating polymer networks of polyurethane and unsaturated polyester were prepared by reaction injection molding (RIM) and transfer molding. The structures of the molded samples were analyzed by electron microscopy and dynamic mechanical analysis. It was found that polymer morphology and dynamic mechanical properties depend strongly on the molding temperature, reaction rate and reaction sequence. Simplified structure models based on Takayanagi's model and sample morphology can predict the storage modulus reasonably well but not the tanδ.     

Polyurethane—polystyrene interpenetrating polymer networks

Two component interpenetrating polymer networks (IPN) of the SIN type (simultaneous interpenetrating networks), composed of a polystyrene network (crosslinked with divinyl benzene) and a polyester-polyurethane network (crosslinked with trimethylolpropane), were made. Electron microscopy and glass-transition measurements showed that phase separation had resulted with some interpenetration, presumably occurring at the boundaries. At a composition of about 75 percent polyurethane, a phase inversion occurred, the continuous phase being polystyrene at polyurethane compositions of less than 75 percent. The stress-strain properties and hardness measurements agreed with these results. Enhanced tensile strength was observed in the IPN's in a concentration range where modulus reinforcement was not evident. A small enhancement in tear strength and thermal stability was also noted.     

Two and three component interpenetrating polymer networks

Two and three component interpenetrating polymer networks (IPNs) have been prepared from polyurethanes, epoxy resins, and acrylic copolymers using the simultaneous technique (SIN). These materials exhibited a variety of morphologies and properties dependent on the types of polymer, molecular weight of precursors, presence of charge groups, and presence of intentional grafts between the component polymer networks. In general, decreasing molecular weight of prepolymers, presence of intentional grafts, and presence of charge groups of opposite charge resulted in increased homogeneity (interpenetration). In addition, increased homogeneity resulted in enhanced mechanical properties.     

互穿聚合物网络研究进展

综述了互穿聚合物网络（ＩＰＮ）研究的进展，介绍了ＩＰＮ在体系，表征，应用等方面的新动向。