聚醋酸乙烯酯/聚丙烯酸甲酯互穿聚合物网络的研究

Interpenetrating Polymer Network-IPN是六十年代初开始发展起来的一种新的化学共混方法。对它在基础和应用开发等方面的研究都有着重要的意义。目前，在IPN的研究领域内，还存在着许多没有表征清楚和难以表征的问题。如IPN中互穿缠结的存在及其形态，IPN的微相结构，IPN的结构与性能之间的关系等问题。这固然与IPN体系本身的复杂性和其理论和基础研究不成熟等因素有关，但也是部分地由于没有选择一个较好的IPN体系，能够较系统地对这些问题加以研究。聚醋酸乙烯酯与丙烯酸甲酯的结构单元在化学结构上是同分异构体，因此是一对相容性较好的聚合物。本工作合成了一系列的聚醋酸乙烯酯-聚丙烯酸甲酯LPN，并对这一体系进行了以下几个方面的研究。一、IPN的合成条件对其动态力学性能的影响二、IPN中的网络I和网络II由于互穿缠结而起的强迫互容效应。三、IPN的溶胀行为反其网络间互穿缠结对溶胀行为的影响。四、IPN体系的橡胶态模量反互穿缠结效应对IPN橡胶态模量的影响。用Binder-Frisch模型解释实验结果，并描述互穿缠结链的形态。五、IPN中网络间的互穿缠结效应对其微相结构的稳定作用。我们首次研究了非Millar-IPN的溶胀行为和其橡胶态模量行为。结果表明在IPN中确实存在着网络间的互穿缠结效应，并且证明，对于互穿缠结效应，网络I比网络II起着更为重要的作用。定性地证明Binder-Frisch模型反其互穿缠结熵公式，ΔSent ∝ φ_I~(-2/3)(1-φ_I)~(1/3) N_I~(-1)N_(II)~(-1/2)σ_I~(-2)σ_(II)~(-1)对于IPN体系是合理的。通过改变网络链的运动环境和改变其相容性等实验手段证明IPN中网络的互穿缠结效应对其形态结构有着远程的稳定作用。

聚二丙烯酸聚乙二醇酯/环氧树脂互穿聚合物网络的研究

采用直接酯法合成了聚乙二醇600、聚乙二醇400、三缩四乙二醇的丙烯酸双酯，并用FT-IR、~1H-NMR表征了这些双酯的结构。以AIBN为双酯引发剂，XLA为环氧固化催化剂，采用一步法（Simultaneous）合成了一系列聚二丙烯酸聚乙二醇酯/环氧树脂互穿聚合物网络。用FT-IR表征了两组分间的氢键相互作用。测定了一系列IPN样品的力学性能，并讨论了各种因素对IPN的力学性能的影响。

聚环氧氯丙烷聚氨酯互穿网络聚合物研究

本文通过一步法合成了两大类聚氨酯互穿网络聚合物（IPN）。其中第一组分是用端羟基聚环氧氯丙烷（PECH）与异氰酸酯反应合成的具有低玻璃化转变温度（Tg）、高弹性的聚醚型聚氨酯，另一组分是高Tg、高模量的聚甲基丙烯酸甲酯（PMMA）、聚苯乙烯（PS）或者是这两者的共聚物（P（MMA-co-S））。对合成的IPN进行了详细、系统的研究。

Preparation and Characterization of Interpenetration Polymer Network Films Based on Poly(vinyl alcohol) and Poly(acrylic acid) for Drug Delivery

A series of full interpenetrating polymer network (full-IPN) films of poly(acrylic acid) (PAA)/poly (vinyl alcohol) (PVA) were prepared by radical solution polymerization and sequential IPN technology. Attenuated total reflectance-Fourier transform infrared spectroscopy, swelling properties, mechanical properties, morphology, and glass transition temperature of the films were investigated. FTIR spectra analysis showed that new interaction hydrogen bonds between PVA and PAA were formed. Swelling property of the films in distilled water and different pH buffer solution was studied. Swelling ratio increased with increasing PAA content of IPN films in all media, and swelling ratio decreased with increasing PVA crosslink degree. Tensile strength and elongation at break related not only to the constitution of IPNs but also to the swelling ratio of IPNs.

Fabrication and characterization of microstructured and pH sensitive interpenetrating networks hydrogel films and application in drug delivery field

Novel microstructured and pH sensitive poly(acryliac acid-co-2-hydroxyethyl methacrylate)/poly(vinyl alcohol) (P(AA-co-HEMA)/PVA) interpenetrating network (IPN) hydrogel films were prepared by radical precipitation copolymerization and sequential IPN technology. The first P(AA-co-HEMA) network was synthesized in the present of IPN aqueous solution by radical initiating, then followed by condensation reaction (Glutaraldehyde as crosslinking agent) within the resultant latex, it formed multiple IPN microstructured hydrogel film. The film samples were characterized by IR, SEM and DSC. Swelling and deswelling behaviors and mechanical property showed the novel multiple IPN nanostuctured film had rapid response and good mechanical property. The IPN films were studied as controlled drug delivery material in different pH buffer solution using cationic compound, crystal violet as a model drug.

Preparation and Characterization of Nanostructured and High Transparent Hydrogel Films with pH Sensitivity and Application

Novel nanostructured, high transparent, and pH sensitive poly(2-hydroxyethyl methacrylate-co-methacryliac acid)/poly(vinyl alcohol) (P(HEMA-co-MA)/PVA) interpenetrating polymer network (IPN) hydrogel films were prepared by precipitation copolymerization of aqueous phase and sequential IPN technology. The first P(HEMA-co-MA) network was synthesized in aqueous solution of PVA, then followed by aldol condensation reaction, it formed multiple IPN nanostructured hydrogel film. The film samples were characterized by IR, SEM, DSC, and UV-vis spectrum. The transmittance arrived at 93%. Swelling and deswelling behaviors showed the multiple IPN nanostructured film had rapid response. The mechanical properties of all the IPN films improved than that of PVA film. Using crystal violet as a model drug, the release behaviors of the films were studied.

淀粉和生物降解大分子间的半互穿聚合物网络的耐水性研究

以淀粉和可生物降解的PCL或PHBV等疏水性脂肪族聚酯为原料,制备了淀粉基的Sem i-IPN材料.加入PCL或PHBV等疏水性大分子的使淀粉基Sem i-IPN材料的耐水性能相对于原淀粉有很大的改善,通过热处理和溶剂化作用能使Sem i-IPN的耐水性进一步提高.

SAXS measurements of the interface in polyacrylate and epoxy interpenetrating networks with fractal geometry

The interface thickness in two-component interpenetrating polymer networks (IPN) system based on polyacrylate and epoxy were determined using small-angle X-ray scattering (SAXS) in terms of the theory proposed by Ruland. The thickness was found to be nonexistent for the samples at various compositions and synthesized at variable conditions-temperature and initiator concentration. By viewing the system as a two-phase system with a sharp boundary, the roughness of the interface was described by fractal dimension, D, which slightly varies with composition and synthesis condition. Length scales in which surface fractals are proved to be correct exist for each sample and range from 0.02 to 0.4 Angstrom(-1). The interface in the present IPN system was treated as fractal, which reasonably explained the differences between Pored's law and experimental data, and gained an insight into the interaction between different segments on the interface. (C) 1997 Elsevier Science Ltd.

Dynamic mechanical properties of interpenetrating polymer networks based on polyacrylates and epoxy

Interpenetrating polymer networks (IPNs) based on polyacrylate (poly(polyethylene glycol diacrylate), PEGDA) and epoxy(diglycidyl ether of bisphenol A, DGEBA) were prepared simultaneously Dynamic mechanical properties of the SINs (simultaneous interpenetrating networks) with various compositions were studied. Enhanced mechanical properties were found in this case. From the point of view of pre-swollen networks, all of the PEGDA/DGEBA IPNs were composed of the individual pre-swollen networks. A micro-phase segregation system was produced in the SIN. Glass transition temperatures shifted inward, which was attributed to molecular packing effects or mutual-entanglements of molecular segments among the individual pre-swollen networks. In accordance with the additivity of properties, namely the parallel model, the entanglement density between the two polymer networks reached its maximum at 50/50 PEGDA/DGEBA IPN.

Miscibility, crystallization, and morphology studies of thermosetting polyimide PMR-15/PEK-C blends

Miscibility, crystallization, and mechanical properties of blends of thermosetting polyimide PMR-15 and phenolphthalein poly(ether ketone) (PEK-C) were examined. With the exception of the 90/10 blend, which has two glass transition peaks, all the blends with PMR-15 less than 90 wt % are miscible in the amorphous state according to DMA results. Addition of PEK-C hindered significantly the crystallization of PMR-15, indicating that there must exist some kind of interaction between molecular chains of PMR-15 and those of PEK-C. The semi-IPN system of PMR-15/PEK-C blends exhibits good toughness. Two distinct microphases, interweaving at the phase boundaries, were found in the PMR-15/PEK-C 60/40 blend. The toughness effect of the blends is discussed in terms of the interface adhesion between the two distinct phases and the domain sizes of the phases. The relation between miscibility and toughness of the blends was investigated. (C) 1996 John Wiley & Sons, Inc.

Miscibility and crystallization behavior of thermosetting polyimide thermoplastic polyimide blends

Compatibility, morphology, crystalline structure and mechanical properties of the blends of a thermosetting polyimide with thermoplastic polyimides consisting of dianhydrides of different lengths have been studied by the use of dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and small-angle X-ray scattering (SAXS) techniques. The results of our research show that the blends change from compatible to semi-compatible when the difference between the length of the dianhydrides of the two components increases. Addition of a thermoplastic polyimide inhibits the crystallization of the thermosetting component. However, this effect decreases with increasing length of the dianhydrides and the distribution of the molecules of the thermoplastic polyimide component changes from interlamellar to interfibrillar. Impact strength and morphology of the fractured surfaces indicate that among the semiinterpenetrating polymer networks (semi-IPN) obtained the toughening effect of the partially compatible one is the best. The results are discussed in terms of charge transfer interaction between imide group and p-phenylene group.

聚酰亚胺及其共混物

本文综述了聚酰亚胺及其共混物的研究进展，讨论了聚酰亚胺的分子结构对其共混物的相容性，结晶行为及力学性能的影响。

聚环氧氯丙烷聚氨酯／聚甲基丙烯酸甲酯互穿网络聚合物的相容性与力学性能

用同步法合成了聚环氧氯丙烷聚氨酯／聚甲基丙烯酸甲酯互穿网络聚合物［ＰＵ（ＰＥＣＨ）／ＰＭＭＡＩＰＮ］，调节ＩＰＮ中两组分组成比制备出由完全弹性体、增强弹性体、增韧塑料到脆性塑料多种高聚物合金材料．用ＤＳＣ、动态力学谱、ＴＥＭ对ＩＰＮ的研究结果表明，ＰＵ（ＰＥＣＨ）／ＰＭＭＡＩＰＮ的两组分是完全相容的；同时对各种组成比的ＩＰＮ材料进行力学性能测试，用相容性ＩＰＮ中互穿、缠结结构解释其力学行为，并用ＳＥＭ对断面形貌进行了观察解释．

Studies on polyepichlorohydrin-based polyurethane/poly(MMA-co-St) IPNs

Interpenetrating polymer networks of polyepichlorohydrin-based polyurethane/poly(MMA-co-St) have been prepared with simultaneous mettled by changing the weight fraction of MMA(W-MMA) in copolymer of MMA with styrene. The IPNs have been studied by DSC, TEM and dynamic mechanical spectroscopy(DMS). The results show that the IPNs have only one T-g, when W-MMA is greater than 0. 6. But when W-MMA IMA is less than 0. 4, the IPNs have two T(g)s, and phase separation is observed on TEM. The phenomenon is explained according to the solubility parameters(delta) and the fraction of hydrogen bond(delta(h)) of P (MMA-co-St). The study reveals that there is a close correlation among the delta, domain size and mechanical properties of PU (PECH)/P(MMA-co-St) IPN.

MORPHOLOGY AND DYNAMIC MECHANICAL-PROPERTIES OF AB CROSS-LINKED POLYMERS BASED ON POLYURETHANES

Polyoxypropylene glycol (PPG) (or castor oil) and toluene diisocyanate (TDI) were mixed, and the prepolymer polyurethane (PU) (I) was formed. Vinyl-terminated polyurethane (II) was prepared from (I), and hydroxyethyl acrylate, AB crosslinked polymers (ABCPs) were synthesized from (II) and vinyl monomers such as styrene, methyl methacrylate, vinyl acetate, etc. The dynamic mechanical properties and morphology of ABCPs were measured. The ABCPs based on PPG have double glass transition temperatures (T(g)) on the sigma-vs. temperature curves. They display a two-phase morphology with plastic components forming the continous phase and PU-rich domains forming the separated phase on the electron micrographs. Irregular shapes and a highly polydisperse distribution of PU-rich domain sizes were observed. The crosslink density of ABCPs has a notable effect on the morphology and properties. The average diameter of the PU-rich domains depends on the molecular weight of prepolymer PPG. The highly crosslinked structures will produce large numbers of very small domains. ABCPs based on castor oil show a single T(g) relaxation on the dynamic mechanical spectra. The compatibility between the two components is much better in ABCPs based on castor oil than in those based on PPG, because there is a high crosslink density in the former. Comparison of the dynamic mechanical spectra of ABCP and interpenetrating networks (IPN) based on castor oil with similar crosslink density and composition imply that the two components in ABCP are compatible whereas microphase separation occurs in IPN. An improvement in the compatibility is achieved by the crosslinking between the two networks.