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。     

聚苯硫醚/环氧树脂共混体系的结构流变学

采用熔融共棍的力一法制备r聚笨硫醚州屯氧树脂复合体系(PPS/EPS),用流变学力一法考察r双酚A型环氧树脂对复合体系内基体结钩的影响。结果表明,环氧树脂的加入热氧化引发PPS基体化学交联,随环氧树脂用量的增加交联程度变大。PPS基体交联网络结钩的存在使得复合体系低频区动态模量显著增加,并呈现强烈的非末端效应,且复合体系对稳态剪切的敏感性下降。     

Interpenetrating Polymer Networks of Hydrocarbon and Fluorocarbon Polymers: Epoxy/Fluorinated Acrylic Macromonomers

A fluorinated acrylic resin was synthesized for use as a co‐monomer with a commercially available epoxy resin for UV‐cured interpenetrating polymer network preparation. Hybrid IPN networks were achieved with morphology ranging from a co‐continuous IPN to complete phase separation simply by changing monomer ratios. Highly hydrophobic coatings with good adhesion properties on glass substrates were obtained.

     

环氧树脂改性MDI型聚氨酯弹性体的性能研究

采用聚己二酸乙二醇丙二醇酯（PEPA）和4,4’-二苯基甲烷二异氰酸酯（MDI）为原料合成了聚氨酯预聚体,在预聚体固化剂中掺入环氧树脂,制备了环氧树脂改性MDI型聚氨酯弹性体,并对弹性体的结构和性能进行表征。结果表明,环氧树脂改性MDI型聚氨酯弹性体中存在嗯唑烷酮结构,提高了弹性体的热分解温度和耐热性能,但弹性体的动态性能变差,微相分离程度变弱。     

含有聚醚多胺环氧树脂网络的形态及力学性能

不同相对分子质量聚醚多胺与环氧树脂于６０℃混合后,加入固化剂二乙烯三胺,在８０℃＊ｈ,１２０℃＊４ｈ下固化,可制备含聚醚多胺的固化环氧树脂网络。     

The Influence of Diphenyl Siloxane on Morphology and Physical Properties in the Poly(Imide Siloxane)(PIS) Copolymer

Various numbers of diphenyl-siloxane groups were incorporated in α,ω-bis(aminopropyl)polydimethylsiloxane (APPS) to prepare α,ω-bis(aminopropyl)-polydimethyldiphenylsiloxane (APPPS) oligomers of three different number-average molecular weights(Mn = 547,772,1210 g mol⁻¹).These APPPS oligomers were than used, together with 3,3′,4,4′-bezonphenone tetracarboxylic dianhydride (BTDA) and 2-2′-bis[4-(3-aminophenoxy)phenyl] sulfone (m-BAPS), to synthesize a series of APPPS containing poly(imide siloxane) (PIS) copolymers. Microstructural studies showed that at certain APPPS content, a critical microphase separation point existed, beyond which, microphase separation began to develop. This critical point of microphase separation was found to be affected by the Mn of the APPPS oligomers (8.0, 4.3 and 2.1 mol% for Mn of 547, 772 and 1,210 g mol⁻¹, respectively). Diphenyl-siloxane significantly improved compatibility between polyimide and polysiloxane segments. Physical studies showed that the introduction of diphenyl siloxane changed the thermal stabilities and mechanical properties of the PIS copolymers. These findings have potential applications for design purposes in engineering polymers.     

SAXS Characterization of New Nanocomposites Based on Epoxy Resin/Siloxane/MMA/Acrylic Acid Hybrid Materials

Epoxy anhydride networks were modified with Siloxane/PMMA hybrid materials, obtained from sol/gel method. The effects of thermal annealing of the Siloxane/PMMA hybrids and of the hybrid composition on the nanostructure of the epoxy network were investigated by means of SAXS. The composites containing Siloxane/PMMA materials with low amount of MMA present a hierarchical nanostructure whose first level is made of siloxane nanoparticles spatially correlated in the matrix forming larger secondary hybrid aggregates. Small amounts of hybrid material decrease the glass temperature of the composite, but increase the storage modulus, indicating its nanoreinforcing action.

     

Toughening of Diglycidyl Ether of Bisphenol-A Epoxy Resin Using Poly (Ether Ether Ketone) with Pendent Ditert-Butyl Groups

Poly(ether ether ketone) (PEEKDT), hydroxyl terminated poly(ether ether ketone) (PEEKDTOH) and fluorine terminated poly (ether ether ketone) (PEEKDTF) with pendent ditert-butyl groups were synthesized by the nucleophilic substitution reaction of 4,4′-difluorobenzophenone with 2,5-ditert-butylhydroquinone in N-methyl-2-pyrrolidone medium using anhydrous potassium carbonate as catalyst. Diglycidyl ether of bisphenol-A epoxy resin was blended with PEEKDT, PEEKDTOH, and PEEKDTF, and cured with 4,4′-diaminodiphenylsulfone (DDS). The polymers formed heterogeneous blends before curing, and upon curing the polymers got dispersed in the epoxy matrix. The mechanical properties of the cured blends were slightly lower than that of the unmodified resin. The fracture toughness increased with the addition of ditert-butyl PEEK into epoxy resin and the extent of improvement was dependent on the type of modifier used. Hydroxyl terminated polymers gave up to 40% increase in fracture toughness. The dynamic mechanical spectrum of the blends showed only a single T_g due to the proximity of the glass transition temperature of modified PEEK and DDS cured epoxy resin.     

Study on Curing Kinetics and Thermal Degradation Kinetics of Hyperbranched Poly(Trimellitic Anhydride Ethylene Glycol) Epoxy (HTME)/Diglycidyl Ether of Bisphenol-A Epoxy Hybrid Resin

Hyperbranched poly(trimellitic anhydride ethylene glycol) epoxy (HTME) not only has relatively low viscosity and high molecular weight but also is a functional additive of enhancement and toughness and is used in the thermosetting resin field widely. The curing kinetics and thermal degradation kinetics of HTME/diglycidyl ether of bisphenol-A epoxy hybrid resin were studied in detail using differential scanning calorimetry and thermogravimetric analysis technique, respectively, by the Coats-Redfern model. The effect of molecular weight or generation and content of HTME on activation energy, reaction order, curing time, and curing reaction were discussed and analyzed, and the results indicated that HTME could accelerate curing reaction and reduce activation energy and reaction order of the curing reaction.     

Synthesis and Properties of Interpenetrating Polymer Networks Composed of Epoxy Resins and Polysulphones with Cross-linkable Pendant Vinylbenzyl Groups

Polysulphones with cross-linkable pendant vinylbenzyl groups (PSF-VB) were prepared via chloromethylation of commercial polysulphones. The curing reactivity of PSF-VB was investigated by differential scanning calori-metry. Interpenetrating polymer networks (IPNs) were prepared based on bisphenol A diglycidyl ether (DGEBA) and PSF-VB, where DGEBA was cured by 4,4′-diaminodiphenyl sulphone and VB groups of PSF-VB were radically polymerized using dicumyl peroxide (DCP). Polysulphones having pendant benzyl groups (PSF-Bz) were also prepared and used as non-reactive modifiers. The fracture toughness (K_IC) for the resulting epoxy/PSF-VB IPN increased by 65% with no loss of mechanical properties on 10wt% addition of PSF-VB (7·9mol% VB unit, MW 74000). Non-reactive PSF-Bz was less effective than PSF-VB. Although the PSF-Bz modified resin had a particulate structure, the morphologies of the PSF-VB/epoxy IPNs were not clear from scanning electron micrographs. Furthermore, the epoxy/PSF-VB IPNs had higher solvent resistance than the epoxy/PSF-Bz blends. Morphological behaviour, modification results and high solvent resistance of the cured epoxy/PSF-VB resins indicate that cross-linked PSF-VB and the epoxy network entangled fully in the presence of DCP. © of SCI.     

Spherulitic Morphology and Crystallization Kinetics of Poly(vinylidene fluoride)/Poly(vinyl acetate) Blends

Spherulitic morphology and crystallization kinetics of the blends of poly(vinylidene fluoride) (PVDF) and poly(vinyl acetate) (PVAc) prepared by solution casting films have been investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The results suggested that PVAc was mainly segregated into the interlamellar and/or interfibrillar regions due to the volume-filling spherulitic morphology observed. As for the results of crystallization kinetics, it was found that both the PVDF spherulitic growth rate (G ^PVDF) and the overall crystallization rate constant (k _n ) were depressed with either the addition of PVAc component or the increase of crystallization temperature (T _c). The kinetics retardation was attributed to the decrease in PVDF molecular mobility and dilution of PVDF concentration due to the addition of PVAc, which has a higher glass transition temperature (T _g).     

Synthesis and Surface Properties of Poly(methyl methacrylate)/Poly(ethylene glycol) Binary Brushes

A new kind of binary polymer brushes was synthesized from two immiscible polymers, PMMA and PEG, on GPS‐modified silicon wafers. Surface composition, layer thickness, coverage, chain density, wetting ability, morphology and protein adsorption of the binary brushes were investigated by XPS, ellipsometry, AFM and contact angle measurements. The results show that both PMMA and PEG were successfully grafted onto the surface. The surface coverage and the chain density of PMMA and PEG brushes can be controlled by modulating the reaction temperature and time. This kind of binary polymer brushes exhibits a distinct microphase‐separated structure and excellent protein‐preventing property.

     

Lamellar Morphology of Poly(3-hydroxybutyrate)/Poly(ethylene oxide) Blends as Studied via Small Angle X-ray Scattering

The lamellar morphology of a melt-miscible blend consisting of two crystalline constituents, poly(3-hydroxybutyrate) (PHB) and poly(ethylene oxide) (PEO) have been investigated by means of small angle X-ray scattering (SAXS). The blend was a crystalline/amorphous system when temperatures lay between the melting point of PEO (ca. T _m ^PEO=60C) and that of PHB (ca. T _m ^PHB=170C), while it became a crystalline/crystalline system below T _m ^PEO. The crystalline microstructures of the blends were induced by two types of crystallization history, i.e. one-step and two-step crystallizations. In the one-step crystallization, the blends were directly quenched from the melt to room temperature to allow simultaneous PHB and PEO crystallization. The two-step crystallization involved first cooling to 70C to allow PHB crystallization for 72 h followed by cooling to room temperature (ca. 19C) to allow PEO crystallization. In the crystalline/crystalline state, two scattering peaks have been observed in the Lorentz-corrected SAXS profiles, irrespective of the crystallization histories, meaning that crystallization created separate PHB and PEO lamellar stack domains. One-step crystallization yielded lamellar stack domains containing almost pure PHB and PEO lamellae. Two-step crystallization generated almost pure PHB lamellar domains and the PEO lamellar domains with inserted PHB lamellae. In the crystalline/amorphous state, the composition dependence of the amorphous layer thickness (l _a), the presence of zero-angle scattering, and the volume fraction of the PHB lamellar stack (_s) revealed that both one-step and two-step crystallizations, generated the interfibrillar segregation morphology, where the extent of interfibrillar segregation of amorphous PEO increased with increasing PEO content.     

用DSC法研究环氧树脂/环氧封端酚酞聚芳醚腈的固化特性

利用差示扫描量热法研究了AG - 80环氧树脂和环氧封端酚酞聚芳醚腈 (简称E -PCE)共混物中固化剂含量对树脂基体固化反应温度、反应热的影响。此共混环氧树脂基体的最低固化反应温度为1 61 .3℃ ,固化反应表观活化能为 60 .66kJ/mol,固化反应级数为 0 .875。     

聚醚酰亚胺/环氧树脂体系的固化及相分离行为研究

环氧树脂固化物本征的低韧性是限制其在复合材料应用的主要缺点之一。利用高性能热塑性树脂聚醚酰亚胺(PEI)与环氧树脂共混,系统研究了PEI在环氧树脂中的溶解行为、固化行为以及相分离行为。溶解试验表明:PEI与环氧齐聚物具有良好的相互溶解性;同时,PEI的加入降低了环氧树脂固化反应的活化能,但并没有改变其固化反应的机制。扫描电镜结果显示:随着PEI含量的增加,环氧/PEI浇铸体的相形貌从明显的分散颗粒相结构演变为双连续相结构和反转相结构。     

环氧扩链端羧基乳酸预聚物

L-乳酸先熔融缩聚成乳酸预聚物,再以丁二酸酐封端,最后以环氧树脂AG80进行扩链.采用傅里叶红外光谱仪、差示扫描量热仪与热重分析仪对扩链产物进行结构性能表征.探讨丁二酸酐用量、扩链剂用量、催化剂类型与用量、反应条件对扩链反应的影响.结果表明:丁二酸酐用量2.5％,环氧基团/羧基摩尔比1.5:1,催化剂为2-甲基咪唑,催化剂用量1.5％,在160℃下反应10 min时,扩链后聚乳酸粘均分子量达到145600.     

Lamellar Morphology of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/Poly(methyl methacrylate) Blends Probed by Small Angle X-ray Scattering

The lamellar morphology of a melt-miscible blend consisting of random poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P(HB-co-HV)) copolymer containing 10 mol% HV units and poly(methyl methacrylate) (PMMA) prepared by solution casting films have been investigated by means of small angle X-ray scattering (SAXS), differential scanning calorimetry (DSC) and polarized optical microscope (POM). The composition dependence of the amorphous layer thickness (l_a), and the volume fraction of the P(HB-co-HV) lamellar stack (φ_s) revealed that the interfibrillar segregation morphology was generated, where the extent of interfibrillar segregation of PMMA increased with increasing PMMA content. The Lorentz-corrected SAXS profiles of the blends crystallized at T_c=40 ^○C has observed “zero-angle scattering”, attributed to the electron density contrast between the lamellar stack domains consisting of alternating crystalline/amorphous layers and the PMMA-rich domains located outside the lamellar stack domains.     

Morphology,dynamic mechanical,and electrical properties of bio‐based poly(trimethylene terephthalate) blends,part 1: Poly(trimethylene terephthalate)/poly(ether esteramide)/polyethylene glycol 400 bis(2‐ethylhexanoate) blends

Bio‐based PTT and PTT blends with PEEA of two different ion contents (275 ppm Na and 3515 ppm Na) and PEG 400 bis (2‐ethylhexanoate) were prepared by melt processing. The blends were characterized by differential scanning calorimetry, dynamic mechanical analysis, transmission electron microscopy, and atomic force microscopy. Electro‐static performance was also investigated for those PTT blends since PEEA is known as an ion conductive polymer. Here we confirmed that PEG 400 bis (2‐ethylhexanoate) improves the static decay performance of PTT/PEEA blends. DMA strongly suggests that PEG 400 bis (2‐ethylhexanoate) and PEEA are miscible pairs, and PEG 400 bis (2‐ethylhexanoate) selectively goes into the PEEA phase rather than the PTT phase, which lowers the T_g of PEEA. Besides topographic analysis of morphology and phase separation, tunneling atomic force microscopy was also applied to see if we can observe the surface directly for the static dissipative material. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and thermal properties of PU/P(BMI–UBMI) IPNs

The preparation of polyurethane/poly(bismaleimide–urethane bismaleimide) [PU/P(BMI–UBMI)] IPNs were carried out in two steps. The two-network interaction and the morphology of PU/P(BMI–UBMI) IPNs were characterized by FTIR and TEM. The effect of the interpenetration of P(BMI–UBMI) and PU on the hydrogen bonds of N—H and the pyrolysis procedure of PU/P(BMI–UBMI) IPNs were investigated by DSC and TG. The results indicate that the interpenetration of P(BMI–UBMI) and PU reinforces the hydrogen bonding of N—H, and the incorporating of UBMI enhances the compatibility of the two networks, leading to ideal interpenetrating, which weakens the force constant of C—N—C in maleimide rings. The morphology of PU/P(BMI–UBMI) IPNs shows multiphase domains which have an obvious phase interface. The domains are connected to each other and the domain dimensions are far smaller than those of PU. The thermal weight loss shows obvious stages at different pyrolysis periods. The thermal stability of PU/P(BMI–UBMI) IPNs are much better than that of PU given the content and crosslink density of P(BMI–UBMI) in a certain range. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1689–1694, 1998     

PPE/EP体系的形态、固化行为和耐热性研究

用等温差示扫描量热法和红外光谱(FT-IR)研究了聚苯醚(PPE)/环氧树脂(EP)体系的固化反应,得出了固化反应程度与反应时间的关系曲线,结果表明在所研究的温度范围内,等温固化温度越高,PPE/EP体系的反应速率越快,最终的反应程度越高.红外的研究结果表明,在180℃固化2 h后,EP不能固化完全,这是由于在固化过程中,伴随着体系的凝胶及EP分子量的逐步增加,引起体系的粘度增大所致.采用扫瞄电子显微镜和综合热分析仪,分别研究了PPE/EP混合物固化材料的形态和耐热性.研究结果表明在PPE/EP体系中加入TAIC(triallylisocyanurate)可有效地提高体系的耐化学药品性,但体系的耐热性也将随着TAIC的加入降低;PPE/EP混合物的耐热性随着PPE含量的增加而提高.