Polyurethane-crosslinked epoxy resins. I. Mechanical behavior

Polyurethane (PU) prepolymers based on poly(butylene adipate) (PBA) and poly(oxytetramethylene) (PTMO) polyols were employed as a crosslinking agent to the diglycidyl ether of bisphenol A (DGEBA). Then the DGEBA was cured with a tertiary amine catalyst to form PU-crosslinked DGEBA. The tensile strength of both the PU(PBA)-crosslinked DGEBA and PU(PTMO)-crosslinked DGEBA systems increased to a maximum value with increasing PU content in the system and then decreased with further increasing PU content. Izod impact property of these PU-crosslinked DGEBA indicated that the PU(PBA)-crosslinked DGEBA had much more significant improvement than the PU(PTMO)-crosslinked DGEBA. On the contrary, the fracture energy (G_{1 C} value) of the resultant PU-crosslinked DGEBA showed that the PU(PTMO)-crosslinked DGEBA had much higher G_{1 C} values than the PU(PBA)-crosslinked DGEBA.     

Interpenetrating polymer networks of polyurethanes and epoxy resin,II. Compatibility and morphology

The interpenetrating polymer networks (IPN) of polyurethanes (PU) and a glycidyl ether of phenol formaldehyde (GEPF) were prepared by a simultaneous polymerization method. The dynamic mechanical properties and morphologies of the IPNs were investigated. It was found that multiphased morphology was formed in the PU/GEPF IPNs. With the PU based on polyester- or polyether-type polyols, the dynamic mechanical analysis (DMA) of these IPNs exhibited various shifts in the loss moduli (E″) of the high and low temperature transition domains depending upon the types and molecular weights of the polyols employed in the PU. Three distinct transition domains were observed as the PU content increased up to a certain level.     

Interpenetrating polymer networks of bismaleimide and polyether polyurethane–crosslinked epoxy

In this work, we prepared the interpenetrating polymer networks of bismaleimide and polyether-type polyurethane(polyoxypropylene)–crosslinked epoxy (BMI/PU(PPG)–EP IPNs) by employing the simultaneous bulk polymerization technique. The polyurethane (PU)–crosslinked epoxy was identified via infrared (IR) spectra analysis. Also investigated herein were the mechanical properties, including tensile strength, Izod impact strength, and fracture energy (G_IC) of the IPNs with various BMI contents in PU–crosslinked epoxy matrix. In addition, differential scanning calorimetry (DSC) analysis and the thermogravimetric analysis (TGA) were performed to examine the thermal properties of the BMI/PU(PPG)–EP IPNs. In addition, morphology and dynamic mechanical analysis (DMA) of the BMI/PU(PPG)–EP IPNs were also studied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2635–2645, 1998     

Study on epoxy resins modified by polycarbonate polyurethanes

In this article, the structure and properties of the epoxy resin (EP) modified by polyurethane (PU) prepolymers were studied. The three types of polyurethane prepolymers, namely, polycarbonate-type PU (TPC), polyether-type PU, and polycarbonate–polyether-type PU were employed. The samples were analyzed by means of an infrared spectrometer, a differential scanning calorimeter, a scanning electron microscope, a transmission electron microscope, a scanning tunnel microscope, and a thermal gravimeter. The results show that the EP modified by TPC is of excellent thermal resistance and mechanical properties. Specifically, when the ratio of PU to EP is 10/100 (wt/wt), optimal properties are achieved. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 887–893, 1998     

Polystyrene and polyether polyurethane elastomer blends compatibilized by SMA: Morphology and mechanical properties

Blends of polystyrene (PS) and the polyether polyurethane elastomer (PU‐et) were prepared by melt mixing using poly(styrene‐co‐maleic anhydride) (SMA) containing 7 wt % of maleic anhydride as a compatibilizer. The polyurethane in the blends was crosslinked using dicumyl peroxide or sulfur. The content of maleic anhydride was varied in the blends through the addition of different SMA amounts. The morphology of the blends was analyzed by SEM and a drastic reduction of both the domain size and its distribution was observed with increase of the anhydride content in the blends. The morphology of the PU‐et blends also showed dependence on the crosslinker agent used for the elastomer, and larger domains were obtained for the elastomer phase crosslinked with dicumyl peroxide. The mechanical properties of the blends were evaluated by flexural and impact strength tests. The blend containing 0.5 wt % of maleic anhydride and 20 wt % of PU‐et crosslinked with sulfur showed the highest strength impact, which was three times superior to the PS strength impact, and the blends containing 20 wt % of PU‐et crosslinked with dicumyl peroxide showed the highest deflection at break independent of the anhydride content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 830–837, 2002     

Crosslinking reaction of epoxy resin (diglycidyl ether of bisphenol A) by anionically polymerized polycaprolactam: I. Mechanism and optimization

Different ratios of epoxy resin, diglycidyl ether of bisphenol A (DGEBA) and ?‐caprolactam (starting from 10:90 DGEBA and vice versa), were used to synthesize reactive DGEBA and polycaprolactam blends by the anionic polymerization of ?‐caprolactam at 140°C. Anionic polymerization was conducted with a strong base such as sodium hydride as a catalyst along with a cocatalyst such as N‐acetyl caprolactam. The reaction mechanism, possible cure reactions, and reaction conditions of the reactive blends were studied with Fourier transform infrared spectroscopy and differential scanning calorimetry. The experiments were carried to study the optimization ratio and the effect of the composition on properties such as hardness and tensile strength of the reactive blends. The DGEBA was crosslinked by polycaprolactam through the reaction of the oxirane group with the amide nitrogen, and the reaction was very fast. A ratio of 80:20 (DGEBA:?‐caprolactam) was optimum, and the resulting blend showed the highest tensile strength and hardness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3237–3247, 2003     

Studies on interpentrating polymer networks of polyurethane and polybismaleimide. I. Polyurethane and bismaleimide-urethane copolymer

The interpenetrating polymer networks (IPNs) of polyurethane (PU) and the mixture of bismaleimide (BMI) and the 2-hydroxylethyl methacrylate (HEMA)-terminated PU prepolymer (HPU) were prepared by using a simultaneous polymerization technique. The effects of the PU molecular weight and the amounts of the PU on the mechanical properties, thermal stability, and dynamic mechanical properties are discussed. The IPNs exhibited superior ultimate tensile strength as the polyol of PU and HPU in the IPNs is based on poly(tetramethylene oxide) (PTMO) glycol of molecular weight 1000 (PTMO1000). Izod impact property of the IPNs indicated that the PU(PTMO1000)/BMI-HPU(PTMO1000) IPNs had much more significant improvement than that of the PU(PTM02000)/BMI-HPU(PTMO2000) IPNs. Better thermal stability was shown by the IPNs as compared with the components of the networks, i.e. PU or BMI-HPU copolymers. The dynamic mechanical analysis (DMA) indicates that these IPNs show various shifts in the loss moduli(E) at the high and low temperature transition peaks for various molecular weight of the polyol employed in the PU. Better compatibility between BMI and PU was found as the PU(PTMO1000) was employed.To whom all correspondence should be addressed.     

Damping properties of interpenetrating polymer networks of polyurethane‐modified epoxy and polyurethanes

Interpenetrating polymer networks (IPNs) were prepared from polyurethane (PU)‐modified epoxy with different molecular weight of polyol and polyurethanes based on the mixture of polydiol and polytriol by a one‐shot method. Two types of PU‐modified epoxy: PU‐crosslinked epoxy and PU‐dangled epoxy were synthesized, and the effects of the different molecular weights of polyol in the PU‐modified epoxy/PU IPNs on the dynamic mechanical properties, morphology, and damping behavior were investigated. The results show that the damping ability is enhanced through the introduction of PU‐modified epoxy into the PU matrix to form the IPN structure. As the molecular weight of polyol in PU‐modified epoxy increases, the loss area (LA) of the two types of the IPNs increases. PU‐dangled epoxy/PU IPNs exhibit much higher damping property than that of the PU‐crosslinked epoxy/PU IPNs with 20 wt % of PU‐crosslinked epoxy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 328–335, 1999     

Dependence of dynamic mechanical behavior of DGEBA/DDM stoichiometric epoxy systems on the conditions of curing process

Dynamic viscoelastic properties of diglycidyl ether of bisphenol A (DGEBA) cured with diaminodiphenylemethane (DDM) have been studied. The relaxation spectra of stoichiometric mixtures have been investigated as a function of the casting procedure and the thermal history during curing. Variations on the temperatures of the loss peaks and also on their magnitude have been observed when a solvent was employed to cast the mixtures. These variations have been attributed to the existence of high crosslinked regions formed at the earlier stage of curing inside the overall matrix. The results obtained from mixtures cured with different thermal histories underline the importance of adequate selection of curing conditions in order to obtain the optimum properties for these materials. Differences in crosslink density amongst the mixtures cured at different conditions have been correlated to the extent of reaction obtained by infrared measurements. © 1995 John Wiley & Sons, Inc.     

Modification of aqueous polyurethanes via latex AB crosslinked polymers

A series of Latex AB crosslinked polymers have been synthesized from polyurethane (PU) (polymer A) and polystyrene (PS) (polymer B). The effect of PU/PS composition, crosslinking density in the PS domain, as well as in PU has been studied in terms of dispersion size, TEM morphology, mechanical, dynamic mechanical properties, in addition to swellability in water and toluene of the dispersion cast film. An inverted core (PS)‐shell (PU) morphology with very fine (tens of nanometers) dispersion was obtained, and the film properties were well controlled by the Latex composition and crosslinking density of both phases. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1315–1322, 2001     

Reactive blends of epoxy resin (DGEBA) crosslinked by anionically polymerized polycaprolactam. II. Mechanical and electrical properties

Various reactive blends of diglycidyl ether of bisphenol A (DGEBA)/polycaprolactam were synthesized by anionic polymerization at 140°C, conducted by sodium hydride catalyst, a strong base, along with N‐acetyl caprolactam as a cocatalyst. The experiments were performed to study the effect of composition on the mechanical and electrical properties of the reactive blends, such as tensile properties, flexural properties, Izod impact strength, Rockwell hardness, and volume resistivity. It was observed that the DGEBA was crosslinked by the polycaprolactam through the rapid reaction of the oxirane group with amide nitrogen. The heat of reaction and heat‐deflection temperature of the reactive blends increased with increasing DGEBA content from 50 to 80 wt %, and increased dramatically above 70 wt % DGEBA content. The mechanical and electrical properties of the reactive blends increased with increasing DGEBA content from 50 to 80 wt %. Substantial increases in these properties were observed above 70 wt % DGEBA content in the reactive blends. SEM studies revealed that the reactive blends show a multiphase system with an increase in the DGEBA content from 50 to 80 wt % as the mixing of the two phases increased. The reactive blend Ep₈₀Ca₂₀, with 80 wt % DGEBA content, resembles a single‐phase system because of better mixing of the two phases; as a result, this reactive blend showed the highest mechanical and electrical properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 537–549, 2005     

Effect of charge groups in polyurethane and polystyrene interpenetrating polymer networks

Opposite charges, namely tertiary amine and carboxyl groups, were introduced into polyurethane (PU) and polystyrene (PS), respectively, to prepare PU/PS interpenetrating polymer networks (IPNs) by means of simultaneous bulk polymerization. Four IPNs were synthesized: a full-IPN, two semi-IPNs and a linear blend. The effect of charge groups on the mechanical properties and morphology of the four polymer alloys was investigated. It is found that the PU/PS IPN which was incorporated with charge groups is free of any phase-separation, and sufficiently uniformly distributed, as can be seen from the corresponding scanning electron microscopy (SEM) photographs. Dynamic mechanical analysis indicates that the transition peak of the loss modulus E″ will move towards the centre between the two transition peaks of both components in the absence of charge groups, as a function of an increase in the contents of the opposite charge groups. Meanwhile the storage modulus E′ will decrease in a single-stage way from the previous two-stage mode. The tensile strength in all the four polymer alloys increased markedly along with an increase in the contents of acrylic acid (AA) in the poly(styrene-acrylic acid) (PSAA), which clearly can be seen for the PU/PSAA full-IPN.     

Fracture toughness of polysulfone/epoxy semi-IPN with morphology spectrum

The fracture toughness of the semi-IPN's of crosslinked epoxy and linear polysulfone(PSf) having morphology spectrum was investigated. The epoxy resin was based on diglycidyl ether of bisphenol A(DGEBA) and diaminodiphenylsulfone(DDS). The morphology spectrum, which has the gradual change of the morphological feature resulting from the concentration gradient of PSf in the epoxy resin can be obtained by inserting a PSf film in DGEBA/DDS mixture before cure. The relative rate of the dissolution of the PSf in the epoxy oligomer and the rate of curing reaction determine the concentration gradient of the PSf. In the region where the PSf concentration is less then 5%, sea(epoxy)-island(PSf) morphology is observed. As the concentration of PSf increases, the morphology changes to nodular structure, inverted sea-island, and PSf/epoxy homogeneous phase. Up to overall 10wt% of PSf, the fracture toughness of the PSf modified epoxy with morphology spectrum was higher than that of the counterpart with uniform concentration of PSf. These results were ascribed to the plastic deformation of the continuous PSf rich phase which was present in the morphology spectrum. Received: 13 October 1998/Revised version: 15 December 1998/Accepted: 16 December 1998     

Polyaniline/polyurethane networks. II. A spectroscopic study

The interconnection of polyaniline (Pani) chains through polyurethane (PU) blocks of the same length but with different spacing has originated a series of new semi conducting networks of varying crosslinking density, with good mechanical properties. FTIR, UV-Vis-NIR, XPS and EPR were used to probe the molecular features of the conducting species, and to test the morphological model proposed in a previous publication, where a continuous Pani phase percolates a PU matrix, linked together by a mixed interphase. Blends with the same composition of the networks and a model structure of crosslinked Pani were also prepared for comparison purposes. The proposed morphological model was confirmed by the new findings obtained by the spectroscopic techniques. The differences between the blends and networks of the same composition were discussed in terms of the morphology presented by each of these systems.     

Crosslinking of epoxy-polysiloxane system by reactive blending

The epoxy-polysiloxane network was prepared by reactive blending of poly[(3-aminopropyl)methylsiloxane] (PAMS) containing pendant amino groups and diglycidyl ether of Bisphenol A (DGEBA). The initially immiscible blend is compatibilized during the reaction and crosslinked. Network formation, dynamics of the system and evolution of morphology were determined by dynamic mechanical analysis and light scattering techniques. The grafting epoxy-amine reaction involves a high extent of cyclization resulting in a high fraction of the sol in the networks. Dynamic light scattering data analysis reveals fast and slow relaxation modes of reacting species in the pregel and one single mode in the post-gel state. The network with a stoichiometric composition shows the most homogeneous morphology with a single glass transition temperature. On the contrary, the networks with excess of PAMS are strongly phase-separated exhibiting the unreacted PAMS-rich phase, PAMS phase partly grafted with epoxide and PAMS-DGEBA crosslinked phase.     

Toughening epoxy resins with solid acrylonitrile–butadiene rubber

The feasibility of using solid acrylonitrile–butadiene rubbers (NBR) with 19 and 33% w/w acrylonitrile to toughen diglycidyl ether of bisphenol A (DGEBA) epoxy resins has been investigated. Thermal analysis experiments revealed a two‐phase morphology of these rubber‐modified epoxies. However, the higher content of acrylonitrile in the rubber caused better compatibility between NBR and the epoxy resin. The rubber with 33% acrylonitrile was found to be an effective toughening agent for DGEBA epoxy resins. Fracture surface studies and also the high tensile strength of crosslinked high molecular weight NBR suggest that the toughening effect should arise from rubber bridging and tearing mechanisms. © 2000 Society of Chemical Industry     

Synthesis and properties of self‐crosslinkable polyurethane–urea with silsesquioxane formation

Based on the typical two‐step polyurethane–urea synthesis, a new series of self‐crosslinkable polyurethane (PU)–urea formulations, consisting of poly(tetramethylene oxide) and 4,4′‐diphenyl methane diisocyanate, and extended by ethylenediamine (EDA)/aminoethylaminopropyltrimethyoxysilane (AEAPS), were prepared. FTIR, ESCA, WAXD, DSC, and mechanical properties of samples were recorded. The results show that the self‐crosslinkable polyurethane–urea could be crosslinked by hydrolysis of the trimethyloxysiloxane group to form the silsesquioxane structure. These structures represent a kind of nanosize, cagelike, chemical crosslink site as well as filler, which affect the properties of PU. The morphology, varied with different ratios of EDA/AEAPS, was also discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 190–195, 2004     

双组分低密度聚酯型聚氨酯鞋底原液的研制

以己二酸、乙二醇、一缩二乙二醇和自制的复合催化剂等为原料,合成了聚酯多元醇;进一步以自制的聚酯多元醇和MD I等为原料,制备了双组分低密度聚酯型聚氨酯鞋底原液,并讨论了密度、温度等对鞋底原液性能的影响。应用结果表明,PU鞋底的撕裂强度、耐折性、拉伸强度等性能指标均达到预期的要求。     

Study of a compatibilized ultra-high-molecular-weight polyethylene and polyurethane blend

Ultra-high-molecular-weight polyethylene (UHMWPE) and thermoplastic polyester-type polyurethane (PU) were blended with polyethylene-grafted maleic anhydride (PE-g-MAH) added as a compatibilizer. A dual roller was used as a mixer, and all specimens were produced by the compression molding method. It was found that without compatibilizer, UHMWPE and PU were immiscible polymers and mixing PE-g-MAH reduced the size of the dispersed PU domains by a factor of 10 to reach 0.5–5 μm and caused a more uniform distribution of the PU phase in the UHMWPE matrix. Also, PE-g-MAH influenced the crystallinity of UHMWPE, increased the amorphous region in the UHMWPE phase, and improved interfacial adhesion. The threshold concentration of compatibilizer was 10 wt %, and the compatibilized UHMWPE/PU composites had improved mechanical properties and lower wear rate than the uncompatibilized composite. At some ratio points, compatibilizer composites even had better wear-resistance properties than pure UHMWPE. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3290–3295, 2001     

Rubber modified epoxy resin. II: Phase separation behavior

DGEBA (diglycidyl ether of bisphenol A)–ATBN (amine terminated butadiene acrylonitrile copolymer) blends exhibited upper critical solution temperature (UCST) behavior. Triethylene tetramine (TETA) was introduced as an amine curing agent of epoxy. The real-time phase separation behavior of ATBN-added epoxy system during cure was investigated using laser light scattering. SEM (scanning electron microscopy) and optical microscopy were also employed to observe the morphology of the epoxy blends. Since the DGEBA–ATBN blends showed UCST behavior, the degree of phase separation when cured at low temperature was higher than that when cured at high temperature. The domain correlation length increased as the curing temperature was lowered. Dynamic mechanical analysis (DMA) results indicated that the phase inversion occurred above 20 wt% of ATBN composition.