网络间含离子键的聚氨酯/接枝乙烯基酯树脂互穿聚合物网络 研究

分别以双酚-A型环氧树脂E-51和聚醚型环氧树脂E-46为原料合成了两种二乙胺-环氧树脂和加成多元醇(分别命名为AE-51,AE-46),将其和甲基丙烯酸一起用于合成聚氨酯/接枝乙烯基酯树脂(PU/接枝VER)互穿聚合物网络(IPN),使之在两个网络间形成离子键。实验结果表明,这类新型的IPN材料中两个网络间的互穿程度与相容性进一步提高,从而导致刚性的接枝VER对弹性的PU网络有更好的增强效果。DSC和FTIR的测定结果表明,在含AE-51的IPN中,由于离子键的作用使PU网络硬段的有序结构遭到很大程度的破坏,与AE-51和PU网络中的硬段以及VER网络有较好的相容性有关,因此这类IPN材料具有较好的力学性能。     

Cyanate ester resin/graphene nanocomposite: Curing dynamics and network formation

The curing dynamics and network formation of cyanate ester resin/graphene oxide (GO) nanocomposites were studied by means of Differential Scanning Calorimetry (DSC), Fourier Transform Infrared (FT-IR) and Raman spectroscopies. The incorporation of GO into the resin showed a strong catalytic effect on the cure of the resin, especially in the initial stages. Addition of 4 wt.% GO resulted in the decrease of curing temperature significantly about 97 °C. Activation energy of the nanocomposites also maintained at a low level till the end of the cure. The most effective catalytic behavior was observed with 1 wt.% GO. Both FT-IR and Raman spectra revealed that OH group in GO reacted with cyanate group OCN in the resin to form O(CNH)O bond in the early stages of the cure. These results could provide a low temperature curing route for cyanate ester resins with improved curing efficiency.     

聚氨酯/环氧树脂互穿网络聚合物的性能研究

互穿聚合物网络（Interpenetrating polymer net-work,简称IPN）广泛应用的为聚氨酯基的互穿网络聚合物。其合成多集中在弹性体方面。本文用同步法合成的聚氨酯／环氧树脂互穿网络硬质泡沫塑料材料（简称PU／ERIPNF）,机械性能较好,并研究了其动态力学性能及形态变化。     

聚氨酯与接枝乙烯基酯树脂互穿网络研究: 自由基共聚 单体的影响

通过分子设计技术合成了两种侧链种类和长度可能控制的接枝乙烯基酯树脂(VER),并用它们与聚氨酯(PU)形成了同步互穿网络(SIN)。通过DSC,SEM,TEM,FTIR等考察了接枝VER的共聚单体对VERSIN的形态结构与力学性能的影响。研究结果表明,用甲基丙烯酸甲酯(MMA)为共聚单体的接枝VER网络中的MMA链段与PU网络中的硬段有较好的相容性,导致这类PU/接枝VERSIN中两个网络间的相容性和互穿程度好于由苯乙烯为共聚单体时合成4SIN。因此,在这两类共聚单体合成的SIN中,由MMA形成的接枝VER网络增强PU网络的效果更为显著。     

Graft interpenetrating polymer networks composed of epoxy resin and urethane acrylate resin

For enhancing the interpenetratoin and/or compatibility of the simultaneous interpenetrating networks (SINs) composed of epoxy resin (epoxy) and urethane acrylate resin (UAR), the graft epoxy consisting of different lengths of poly(oxypropylene) (PO) side chains were synthesized and characterized. It was found that the graft epoxy composed of short PO side chains [MW 480, epoxy-g-PO(480)] showed a compatible system while if consisting of longer PO grafts [MW 950, epoxy-g-PO(950)] exhibited a partial microphase separation morphology. DSC measurements as well as the SEM or TEM observation indicated that the interpenetration between the two phases for epoxy/UAR SINs including epoxy-g-PO(480) was improved appreciably due to the excellent miscibility between the PO grafts and PO segments existing in the graft epoxy and the UAR network, respectively. In this case, for SIN(80/20) containing 10 wt % of epoxy-g-PO(480) the tensile strength increases by a factor of 2.70 compared with that of pure epoxy network. However, the improvement of interpenetration and/or compatibility between the two networks as well as the mechanical properties for SINs composed of epoxy-g-PO(950) are limited resulting in the partial microphase separation of epoxy-g-PO(950) network's own self. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3568–3574, 1999     

Synthesis and properties of miscible epoxy/acrylic interpenetrating polymer networks

Three series of epoxy/acrylic interpenetrating polymer networks were prepared by the simultaneous polymerization of diglycidyl ether of bisphenol A, crosslinked with an aliphatic diamine, diglycidyl ether of bisphenol A dimethacrylate, bisphenol A dimethacrylate, and diethoxy bisphenol A dimethacrylate. Under the conditions provided it is believed that the two networks form simultaneously but independently. Differential scanning calorimetry and dielectric measurements indicate that these polymer networks are miscible because they exhibit a single, sharp glass transition temperature, the values of which, however, are lower than predicted by the law of mixture. This decrease may be due in part to the dilution of one network by the other and to the resulting breakage of intramolecular interactions. It is also due, in part or in whole, to the presence of solvent and/or monomer impurities that act as plasticizers.     

Effects of organophilic montmorillonite on hydrogen bonding, free volume and glass transition temperature of epoxy resin/polyurethane interpenetrating polymer networks

Epoxy resin nanocomposites containing organophilic montmorillonite (oM) and polyurethane were prepared by adding oM to interpenetrating polymer networks (IPNs) of epoxy resin and polyurethane (EP/PU). The dispersion degree of oM in EP/PU matrix was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Fourier transform infrared spectrometry (FT-IR) showed that strong interactions existed between oM and EP/PU matrix, and oM had some effect on hydrogen bonding of these EP/PU IPNs nanocomposites. Positron annihilation spectroscopy (PALS) and differential scanning calorimetry (DSC) measurements were used to investigate the effect of oM and PU contents on free volume and glass transition temperature (T_g) of these nanocomposites. The PALS and DSC results clearly showed that the presence of oM led to a decrease in the total fractional free volume, which was consistent with increasing T_g upon addition of oM, ascribed to increasing hydrogen bonding in interfacial regions of oM and EP/PU matrix and enhancing the miscibility between EP phase and PU phase. In addition, with increasing PU content, the total fractional free volume increased, corresponding to decreasing T_g.     

Natural and acid-treated attapulgite reinforced soybean oil-based polyurethane/epoxy resin interpenetrating polymer networks

Soybean oil-based polyurethane (PU)/epoxy (EP) interpenetrating polymer network (IPN) nanocomposites were prepared with natural attapulgite (N-ATT) and acid-treated attapulgite (A-ATT). The structure, glass transition, damping properties, thermal stability, mechanical properties and morphology of PU/EP IPN/ATT nanocomposites were characterized by X-ray diffraction (XRD), dynamic mechanical analysis (DMA), thermogravimetric analyzer, universal test machine and scanning electronic microscope (SEM). XRD showed that interaction with PU did not change the crystal structures of ATT. DMA results revealed the addition of ATT improved the glass transition temperature of the soybean oil-based PU/EP IPN, especially for A-ATT. However, the incorporation of ATT slightly decreased the damping properties of the soybean oil-based PU/EP IPN. Tensile tests confirmed that A-ATT had a significant reinforcement effect on the soybean oil-based PU/EP IPN. The tensile strength of the soybean oil-based PU/EP IPN increased by 56% with the addition of 4 mass% A-ATT. SEM demonstrated the relatively uniform dispersion of both N-ATT and A-ATT in the soybean oil-based PU/EP IPN matrix.

     

Thermal,mechanical, and morphological properties of soybean oil-based polyurethane/epoxy resin interpenetrating polymer networks (IPNs)

A series of interpenetrating polymer networks (IPNs) based on epoxy (EP) resin and polyurethane (PU) prepolymer derived from soybean oil-based polyols with different mass ratios were synthesized. The structure, thermal properties, damping properties, tensile properties, and morphology of soybean oil-based PU/EP IPNs were characterized by Fourier-transform infrared spectroscopy, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), universal test machine, and scanning electron microscopy (SEM). DSC and DMA results show that the glass transition temperature of the soybean oil-based PU/EP IPN decreases with the increase of PU prepolymer contents. Soybean oil-based PU/EP IPNs have better damping properties than that of the pure epoxy resin. The tensile strength and modulus of PU/EP IPNs decrease, while elongation at break increases with the increase of PU prepolymer contents. SEM observations reveal that phase separation appears in PU/EP IPNs with higher PU prepolymer contents.     

Structure and properties of polyurethane/polyacrylate latex interpenetrating networks hybrid emulsions

Some new kinds of novel polyurethane (PU)/polyacrylate (PA) latex interpenetrating networks (LIPNs) were synthesized. Firstly PU dispersions were synthesized by self-emulsification polymerization. Then PU/PA LIPNs using PU dispersion as the seed were prepared by soap free emulsion polymerization. The effects of different PU/PA ratios, the blending method and the NCO/OH molar ratio of PU components on PU/PA LIPNs performance were also investigated. The structure and properties of PU/PA LIPNs such as mechanical properties, particle size, morphology of the surface were characterized by dynamic mechanical analysis, scanning electron microscopy, and dynamic light scattering. It was found that PU/PA LIPNs can markedly improve the water resistance and the mechanical properties of PU latex much more than those of PU/PA physical blends due to a great deal of interpenetrating and entangling between PU and PA latex. Moreover, the particle size of PU/PA LIPNs is related to the PA content and NCO/OH molar ratio of PU components: the higher the NCO/OH molar ratio in PU dispersions, the larger is the particle size of PU/PA LIPNs, and the average particle size of PU/PA LIPNs becomes larger with an increase in PA content.     

Synthesis of mesoporous silica and its modification of bismaleimide/cyanate ester resin with improved thermal and dielectric properties

A novel method is proposed to synthesize new mesoporous silica containing amine groups (MPSA), and it was further employed to modify bismaleimide‐dialllyl bisphenol (BD)/cyanate ester (CE) resin to form novel MPSA/BD/CE hybrids; in addition, the typical properties of MPSA/BD/CE were systematically investigated. Results show that these hybrids have very low dielectric constant and loss as well as good thermal properties. Compared with BD/CE resin, all hybrids have not only decreased dielectric constant and loss but also similar dependence of dielectric properties on frequency over the whole frequency from 10 to 10⁶ Hz. Specifically, with the addition of MPSA to BD/CE resin, the dielectric constant reduces from 3.5 to 3.0, and the dielectric loss is only 85% of that of BD/CE resin. Note that all hybrids show better thermal resistance (reflected by higher glass transition temperature, decreased maximum degradation rate, and higher char yield at 800°C) than BD/CE resin. All these differences in macro‐properties are attributed to the different structure between MPSA/BD/CE hybrids and BD/CE resin. Copyright © 2011 John Wiley & Sons, Ltd.     

Viscoelastic properties of nanostructured natural rubber/polystyrene interpenetrating polymer networks

The effects of the blend ratio and initiating system on the viscoelastic properties of nanostructured natural rubber/polystyrene‐based interpenetrating polymer networks (IPNs) were investigated in the temperature range of ?80 to 150 °C. The studies were carried out at different frequencies (100, 50, 10, 1, and 0.1 Hz), and their effects on the damping and storage and loss moduli were analyzed. In all cases, tan δ and the storage and loss moduli showed two distinct transitions corresponding to natural rubber and polystyrene phases, which indicated that the system was not miscible on the molecular level. However, a slight inward shift was observed in the IPNs, with respect to the glass‐transition temperatures (T_g's) of the virgin polymers, showing a certain degree of miscibility or intermixing between the two phases. When the frequency increased from 0.1 to 100 Hz, the T_g values showed a positive shift in all cases. In a comparison of the three initiating systems (dicumyl peroxide, benzoyl peroxide, and azobisisobutyronitrile), the dicumyl peroxide system showed the highest modulus. The morphology of the IPNs was analyzed with transmission electron microscopy. The micrographs indicated that the system was nanostructured. An attempt was made to relate the viscoelastic behavior to the morphology of the IPNs. Various models, such as the series, parallel, Halpin–Tsai, Kerner, Coran, Takayanagi, and Davies models, were used to model the viscoelastic data. The area under the linear loss modulus curve was larger than that obtained by group contribution analysis; this showed that the damping was influenced by the phase morphology, dual‐phase continuity, and crosslinking of the phases. Finally, the homogeneity of the system was further evaluated with Cole–Cole analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1680–1696, 2003     

Synthesis and characterization of interpenetrating polymer networks with nonlinear optical properties

We report the synthesis and characterization of interpenetrating polymer networks (IPNs) exhibiting nonlinear optical (NLO) properties. The network consists of aliphatic polycarbonate urethane (PCU) and poly(methyl methacrylate-co-N,N-disubstituted urea), with a nonlinear optical (NLO) chromophore incorporated into N,N-disubstituted urea. The full IPNs have only one T_g, as determined by differential scanning calorimetry (DSC), together with scanning electron microscopy (SEM) observations, suggest a single phase morphology. The thin films of IPNs are transparent and the unpoled samples produced second harmonic generation (SHG) signals at room temperature. This result indicates that the NLO chromophore is oriented noncentrosymmetrically during the IPN formation process and is tightly held between the permanent entanglements of the two component networks of the IPN. © 1996 John Wiley & Sons, Inc.     

Preparation and properties of graphene oxide nanosheets/cyanate ester resin composites

Graphene oxide nanosheets (GONSs)/cyanate ester (CE) resin composites were prepared via a solution intercalation method. The structures of the GONSs and the composites were studied using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The mechanical and tribological properties of the composites were investigated. In addition, the thermal behavior of the composites was characterized by thermogravimetric analysis (TGA). Results show that the GONSs/CE resin composites were successfully prepared. The addition of GONSs is beneficial to improve the mechanical and tribological properties of the composites. Moreover, the composites exhibit better thermal stability in comparison with the CE resin matrix.     

Miscibility and properties of polyurethane/benzyl starch semi‐interpenetrating polymer networks

We successfully prepared a series of transparent materials with semi‐interpenetrating polymer networks (semi‐IPNs) from castor‐oil‐based polyurethane (PU) and benzyl starch (BS). The miscibility, morphology, and properties of the semi‐IPN films were investigated with attenuated total reflection/Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical thermal analysis, scanning electron microscopy, wide‐angle X‐ray diffraction, electron spin resonance (ESR), ultraviolet–visible spectroscopy, and tensile testing. The results revealed that the semi‐IPN films had good or certain miscibility with BS concentrations of 5–70 wt % because of the strong intermolecular interactions between PU and BS. With an increase in the concentration of BS, the tensile strength and Young's modulus of the semi‐IPN materials increased. The ESR data confirmed that the segment volume of PU in the semi‐IPNs increased with the addition of BS; that is, the chain stiffness increased as a result of strong interactions between PU and BS macromolecules. It was concluded that starch derivatives containing benzyl groups in the side chains more easily penetrated the PU networks to form semi‐IPNs than those containing aliphatic groups, and this led to improved properties. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 603–615, 2005     

Damping characteristics and mechanical properties of silica filled PUR/PEMA simultaneous interpenetrating polymer networks

Simultaneous polyurethane/poly(ethyl methacrylate) interpenetrating polymer network was synthesised by the one-shot route at the 70PUR/30PEMA composition ratio. This semi-miscible IPN exhibited its potential as a material for damping application by a broad loss factor (tan δ) ? 0.3 spanning a temperature range of 132 °C. The TEM micrographs revealed a multiphase morphology where the mixing between the two polymers was extensive. Incorporation of silica was made in order to study the effects of filler on the IPN properties in terms of glass transition temperature, dynamic mechanical properties, and mechanical and thermal properties. Dynamic mechanical thermal analysis indicated that the filler enhanced the damping ability of the IPN at certain temperature range. Furthermore, the addition of filler resulted in improved material strength.     

Simulation of phase behavior and mechanical properties of ideal interpenetrating networks

In this work microphase separation in ideal interpenetrating networks as well as its influence on the mechanical properties of the networks has been studied. Structures with long-range order in such networks have not been found to be formed; the reason for this is apparently the weak bonding (physical entanglements) between the subnetworks. The dynamics of the relaxation of interpenetrating networks with highly incompatible subnetworks has been studied and it has been found that the slow rearrangement of phase boundaries during the stretching process has a significant influence on it. Using the analysis of subchains conformations, it has been found that the increase in the stiffness of interpenetrating networks with incompatible subchains occurs due to the irregular tension of subchains related to the presence of big aggregates in the system.     

Synthesis and characterization of crosslinked polydiacetylene and its two-component interpenetrating polymer networks

The synthesis of crosslinked polydiacetylenes and its two-component interpenetrating polymer networks (IPNs) was carried out utilizing its polar and flexible substituent groups. Polydiacetylenes were crosslinked by the formation of allophanate linkages utilizing urethane groups in the substituent groups of the polydiacetylenes. Elemental analysis, DSC, TMA, solvent resistance, and IR spectra are presented as evidence for the formation of crosslinked polydiacetylenes. IPNs of polydiacetylenes and an epoxy resin (diglycidyl ether of bisphenol A) were synthesized by using simultaneous and sequential methods of synthesis. A study of phase morphology of the simultaneous and sequential IPNs was carried out using electron microscopy, TMA, and DSC.