Synthesis and characterization of interpenetrating polymer networks with hyperbranched polymers through thermal-UV dual curing

The aim of this study was to investigate the possibility of using acrylated hyperbranched polyesters (HBP) as UV curable component in dual curing automotive applications. Dual curing is one of possible ways to obtain fast curing, scratch resistant coatings for use in OEM and car refinish applications. Dual curing systems, upon hardening, can give interpenetrating networks (IPNs).     

Curing and mechanical properties of dicyanate/poly(ether sulfone) semi‐interpenetrating polymer networks

Semi‐interpenetrating polymer networks (semi‐IPNs) composed of a dicyanate resin and a poly(ether sulfone) (PES) were prepared, and their curing behavior and mechanical properties were investigated. The curing behavior of the dicyanate/PES semi‐IPN systems catalyzed by an organic metal salt was analyzed. Differential scanning calorimetry was used to study the curing behavior of the semi‐IPN systems. The curing rate of the semi‐IPN systems decreased as the PES content increased. An autocatalytic reaction mechanism was used to analyze the curing reaction of the semi‐IPN systems. The glass‐transition temperature of the semi‐IPNs decreased with increasing PES content. The thermal decomposition behavior of the semi‐IPNs was investigated. The morphology of the semi‐IPNs was investigated with scanning electron microscopy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1079–1084, 2003     

外电场对CER/TMPTMA IPNs形成过程的在线监测

利用自制装置研究了脂环族环氧树脂(CER)/三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)互穿网络聚合物(IPNs)的固化过程.通过在线测试CER/TMPTMA体系固化过程中的交流电阻和电容,发现电阻和电容的变化反映出CER/TMPTMA体系的固化过程是一个分步IPNs的形成过程,而且电阻和电容变化趋势与体系的粘度、离子浓度以及偶极子的数量息息相关.利用自制电极和装置可以远距离在线监测热固性树脂的固化过程,在外磁场干扰下,利用CER/TMPTMA固化体系的电阻波动可以表征体系的固化反应情况.     

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     

A novel approach to interpenetrating networks of epoxy resin and polydimethylsiloxane

A novel methodology for preparing interpenetrating polymer networks (IPNs) between an epoxy resin, diglycidylether of bisphenol A (DGEBA) and polydimethylsiloxane (PDMS) was proposed. The vinyl‐terminated PDMS (vinyl‐PDMS) was partially crosslinked with hydrogen‐containing PDMS (H‐PDMS) and was mixed with DGEBA, modified silica (m‐silica), and a methyl tetrahydrophtalic anhydride (MTHPA) curing agent. Subsequently, the curing reactions of the DGEBA/m‐silica and PDMS were allowed to occur separately and simultaneously leading to an IPN. The m‐silica played a double‐fold role: Cocuring with DGEBA and H‐bonding with the oxygen atoms on the PDMS segments, and thus acted as a compatibilizer between DGEBA and PDMS and promoted the generation of the IPN structure. The resulted partially miscible structure was characterized through the dispersion of silica particles and the glass transition behavior of the samples. The mechanical properties of the IPNs were also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

互穿网络聚合物研究及其应用进展

综述了互穿网络聚合物(IPNs)的分类、结构和制备材料,着重讨论了IPNs在各方面的应用,指出了目前IPNs材料制备存在的问题,并对今后IPNs的制备和研究进行了展望,提出了制备IPNs新思路.     

Interpenetrating networks hydrogels based on hyaluronic acid for drug delivery and tissue engineering

There are several techniques for preparing hydrogel biomaterials. Among these techniques, preparation of interpenetrating polymer networks hydrogel (IPNs) has been more interested during last years. IPNs are fabricated by the incorporation of monomers or polymeric chains in hydrogel network. Natural polymers such as hyaluronic acids have some advantages such as biocompatibility, biodegradability and non-toxicity. In this review, we would have a brief view to the interpenetrating polymer networks hydrogel based on hyaluronic acids and its applications as a drug delivery system and tissue engineering applications.     

On-line monitoring of cycloaliphatic epoxy/acrylate interpenetrating polymer networks formation and characterization of their mechanical properties

The novel interpenetrating polymer networks (IPNs) based on cycloaliphatic epoxy resin (CER) containing cyclohexene oxide groups and tri-functional acrylate, trimethylol-1, 1, 1-propane trimethacrylate (TMPTMA) were synthesized. The formation of the IPNs was on-line monitored by means of polarizing optical microscope, time-resolved light scattering and Fourier transform infrared spectroscopy. The morphological and mechanical properties of the resultant IPNs were investigated and evaluated with scanning electron microscopy (SEM) and dynamical thermal mechanical analysis (DTMA), respectively. The on-line monitoring results showed that during the course of the IPNs formation, the TMPTMA component was cured more quickly than the CER component, leading to the formation of the sequential IPNs. During the early curing stage, there were the phase separation phenomena in the CER/TMPTMA system. The SEM results revealed that although there were some slight phase separation phenomena in the CER/TMPTMA system in the early curing stage, the resultant IPNs displayed the homogeneous structures and did not show the apparent phase separation morphology. The DTMA results revealed that the resulting IPNs exhibited rather higher modulus and denser cross-linking network structure than the neat CER system.     

聚氨酯/环氧树脂互穿网络聚合物反应动力学

通过共混法制备了聚氨酯(PU)/环氧树脂(EP)互穿网络聚合物(IPN),采用示差扫描量热法(DSC)和动态机械分析(DMA)对IPN形成过程中的固化反应动力学及产物IPN的相容性进行了研究,结果表明,m(PU)/m(EP)=10∶6的IPN体系的反应级数为0.95,表观活化能为169.23 kJ/mol;PU/EP IPN只有1个玻璃化转变温度,相容性好。     

Molecular interactions in poly(methacrylic acid)/poly(N‐isopropyl acrylamide) interpenetrating polymer networks

The molecular interactions between the component networks in poly(methacrylic acid)/poly(N‐isopropyl acrylamide) (PMAA/PNIPAAm) interpenetrating polymer networks (IPNs) were investigated using attenuated total reflectance (ATR)‐Fourier transform IR (FTIR) spectroscopy. Hydrogen‐bond formation was noted between the carboxyl groups of PMAA and the amide groups of PNIPAAm. The ATR‐FTIR results showed shifts in the carboxylic and amide groups, indicating the existence of hydrogen bonding between these two individual networks within the IPNs. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1077–1082, 2001     

Filler effect on formation and properties of interpenetrating polymer networks based on polyurethane and polyesteracrylate

The formation processes of unfilled and filled interpenetrating polymer networks (IPNs) and some of their physico-mechanical properties have been investigated. The IPN formation kinetics and the constituent network curing rates determine the rate and degree of microphase separation. This in turn determines the boundary layer composition and structure. Introduction of filler into the IPN during formation affects greatly the crosslinking reaction and the microphase segregation of homopolymers. It has been shown that the degree of phase segregation in filled IPNs differs from that in unfilled ones. All the fillers were found to shorten the time of internal stress appearance and to increase its value for IPNs with predominantly high-modulus component content. Some filled IPNs were shown to have greater thermodynamic stability than unfilled ones.     

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

Full interpenetrating networks (IPNs) and semi‐IPNs of Novolac (phenolic) resin and poly(ethyl methacrylate) (PEMA) were prepared by the sequential mode of synthesis. These were characterized with respect to their mechanical properties, that is, ultimate tensile strength (UTS), percentage elongation at break, modulus, and toughness. Thermal properties were studied by DSC and thermogravimetric analysis (TGA). The morphological features were studied through polarizing light microscopy (PLM). The effects of variation of the blend ratios on the above‐mentioned properties were examined. There was a gradual decrease of modulus and UTS with consequent increases in elongation at break and toughness for both types of IPNs with increasing proportions of PEMA. An inward shift and lowering (with respect to pure phenolic resin) of the glass‐transition temperatures of the IPNs with increasing proportions of PEMA were observed, thus indicating a plasticizing influence of PEMA on the rigid and brittle matrix of crosslinked phenolic resin. The TGA thermograms exhibit two‐step degradation patterns. Although there was an apparent increase in thermal stability at the initial stages, particularly at lower temperatures, a substantial decrease in thermal stability was observed in the regions of higher temperatures. The surface morphology as revealed by PLM clearly indicates two‐phase structures in all the full and semi‐IPNs, irrespective of PEMA content. The matrix–PEMA domain interfaces are quite sharp at higher concentrations of PEMA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 412–420, 2003     

Filled interpenetrating networks: their formation and viscoelastic properties

The kinetics of curing, the microphase separation process (MPS) and the viscoelastic properties of interpenetrating polymer networks (IPNs) based on crosslinked polyurethane and linear poly(butyl methacrylate) were studied in the presence of two fillers—talc and polymeric fine-disperse triethylene glycol dimethacrylate. It was found that introducing filler into the reaction mixture changes the reaction kinetics and degree of microphase separation, which in turn affects the viscoelastic properties of the IPNs. The data obtained by dynamic mechanical spectroscopy and differential scanning calorimetry for filled semi-IPNs and calculations of the degree of segregation of the components show that filler introduction results in MPS inhibition on account of a local increase in viscosity near the solid interface, i.e. compatibility is increased.     

环氧/聚氨酯梯度互穿网络聚合物冲击性能研究

研究了采用梯度IPNs方法提高环氧树脂的冲击性能,设计了新型梯度组分分布数学模型描述梯度组分的分布,采用梯度因子和梯度层数控制梯度IPNs的结构变化。并采用逐层浇铸的方法制备了不同种类的环氧/聚氨酯(EP/PU)梯度互穿网络聚合物(IPNs)材料,同时对其冲击性能进行了研究。研究结果表明,梯度结构的变化对其冲击性能有所影响,梯度层数越多,梯度因子越大,梯度IPNs的冲击强度越大。在质量比相同的情况下,梯度IPNs的冲击性能要高于普通IPNs和环氧。     

The effect of composition and the level of crosslinking of the poly(methylmethacrylate) phase on the properties of natural rubber‐poly(methylmethacrylate) semi‐2 interpenetrating polymer networks

The effects of the PMMA content and the cross‐linker level in the poly(methylmethacrylate) component on the dynamic and physico‐mechanical properties of semi‐2 interpenetrating polymer networks based on natural rubber and poly(methylmethacrylate) were determined. The miscibility of the components in these semi‐2 interpenetrating polymer networks was determined using the loss tangent data, obtained from dynamic mechanical thermal analysis and the interphase contents were calculated from modulated scanning calorimetric data. Some component mixing in these semi‐2 interpenetrating polymer networks was evident from these modulated differential scanning calorimetric and dynamic mechanical thermal analysis data. The degree of component mixing increased with cross‐linker level in the PMMA phase. The PMMA content in the semi‐2 IPNs has a significant effect on the tensile and hysteresis behavior of these semi‐2 interpenetrating polymer networks. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Synthesis and characterization of high performance,transparent interpenetrating polymer networks with polyurethane and poly(methyl methacrylate)

Transparent, interpenetrating polymer network (IPN) materials were synthesized using polyurethane (PU) and poly(methyl methacrylate) (PMMA). PMMA contributed to the transparency and rigidity necessary for use in impact‐resistant applications, whereas PU contributed to toughness. Several factors affecting the physical properties, such as the ratio of PU to PMMA, curing profile, inclusion of different isocyanates for the PU phase, and use of an inhibitor in the PMMA phase, were investigated. Full‐IPNs were synthesized so that the two polymer networks would remain entangled with one another, and domain sizes of each system were reduced, mitigating phase separation. Both simultaneous IPNs, polymerization of monomers occurring at the same time, and sequential IPNs, polymerization of monomers occurring at different temperatures, were synthesized for studying the reaction kinetics and final morphologies. The phase morphology and the final thermal and mechanical properties of the IPNs prepared were evaluated. Findings suggest that samples containing ～80 wt% PMMA, 1,6‐diisocyanatohexane 99+% (DCH), and an inhibitor with the MMA monomer created favorable results in the thermo‐mechanical and optical properties. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

增韧改性环氧树脂互穿网络聚合物的合成与表征

合成了端异氰酸酯/环氧丙烯酸树脂互穿网络聚合物,在环氧树脂交联网络中引入柔性链段,达到增韧的目的。通过改变端异氰酸酯和环氧丙烯酸树脂的组分比,合成不同组成的互穿网络聚合物(IPNs)。借助红外光谱和扫描电镜等分析方法,研究了IPNs的分子混合形态结构。同时采用差热分析法(DSC)测试了聚合物的玻璃化转变温度,结果表明:端异氰酸酯预聚体含量越高,聚合物的玻璃化转变温度越低。对成膜物的力学性能研究表明,INPs的拉伸强度在端异氰酸酯/环氧丙烯酸树脂比例为30:70时,拉伸强度为55.24 MPa,是纯环氧树脂的2.5倍。     

Sorption characterization of poly(vinyl alcohol)/chitosan interpenetrating polymer network hydrogels

Poly(vinyl alcohol) (PVA)/chitosan interpenetrating polymer networks (IPN) were prepared by UV irradiation. The water sorption behavior of the IPNs was measured at various temperatures and humidity levels. The water uptake of IPN13 is greater than that of other IPNs. Vapor sorption behavior is more affected by the density of water vapor than by hydrophilic properties with increasing temperature. Equilibrium water uptake increases as humidity increases, and the increase is more noticeable at high humidity. The sorption system of all IPNs is a relaxation‐controlled mechanism at a relative humidity (RH) of 90%, but it is a Fickian diffusion‐controlled mechanism when the RH is below 50%. With an increase in humidity, the diffusion coefficients were found to increase due to greater penetration of water into the IPNs. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 86–90, 2003     

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