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1.
Hygrothermally decomposed polyurethane (HD‐PUR) of a polyester type was used as an impact modifier in tri‐ and tetrafunctional epoxy (EP) resins. Between 5 and 80 wt % of the PUR modifier was added to the EP prior to its crosslinking with a diamine compound (diaminodiphenyl sulfone, DDS). The mean molecular weight between crosslinks (Mc ) was determined from the rubbery plateau modulus of the dynamic mechanical thermal analysis (DMTA) spectra. The fracture toughness (Kc) and energy (Gc) of the modified resins were determined on static‐loaded compact tension (CT) specimens at ambient temperature. The change in the Kc and Gc as a function of Mc followed the prediction of the rubber elasticity theory. The efficiency of the HD‐PUR modifier was compared with that of a carboxyl‐terminated liquid nitrile rubber (CTBN). Attempts were also made to improve the functionality of the modifier by hygrothermal decomposition of PUR in the presence of glycine and ε‐caprolactam, respectively. DMTA and fractographic results showed that HD‐PUR functions as an active diluent and a phase‐separating additive at the same time. As HD‐PUR can be regarded as an amine‐functionalized rubber, it was used as the hardener (by replacing DDS) in some EP formulations. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1139–1151, 2000  相似文献   

2.
Poly(urethane acrylate) (PUA)/poly(methylmethacrylate) (PMMA) core–shell composite particles were prepared by two-stage emulsion polymerization. The sizes of composite particles could be varied from 25 to 210 nm by introducing polyoxyethylene (POE) groups to the urethane acrylate molecular backbone. Core–shell morphology was identified by investigating the polarity of the surface of the core and shell polymer particles and by measuring the contact angle of the composite particles. A composite particle prepared with relatively small particles (about 20 nm) did not show the core/shell morphology, because the high polar surface of the core polymer particle and the low-stage ratio of the core to the shell cause the formation of a core/shell two-stage latex to be more thermodynamically unstable. The fracture toughness of rubber-toughened PMMA containing PUA/PMMA composite particles increased as the particle sizes decreased and the shell thickness of the composite particles increased. In particular, when the average size of the composite particle was about 43 nm and the stage ratio was 50/50, the fracture toughness of the rubber-toughened PMMA increased more than three times compared with that of pure PMMA. Furthermore, the transparency of toughened PMMA could be maintained up to 91% in the visible spectra range. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2291–2302, 1998  相似文献   

3.
Hybrid modifiers composed of N-phenylmaleimide–styrene copolymers (PMS), and N-phenylmaleimide–styrene–p-hydroxystyrene terpolymers (PMSH) containing pendent p-hydroxyphenyl groups as functionalities, were used to improve the toughness of bisphenol-A diglycidyl ether epoxy resin cured with p,p′-diaminodiphenyl sulphone. The hybrid modifiers were effective in toughening the epoxy resin. When using the modifier composed of 10 wt% PMS (M?w 313000) and 2.5 wt% PMSH (2.5 mol% p-hydroxystyrene units, M?w 316000), the fracture toughness (KIC) for the modified resins increased 100% with no deterioration in the flexural properties and the glass transition temperature. The improvement in toughness of the epoxy resins was attained because of the co-continuous phase structure and the improvement in interfacial adhesion. The toughening mechanism is discussed in terms of the morphological characteristics of the modified epoxy resin systems.  相似文献   

4.
Core–shell structured particles, which comprise the rubbery core and glassy layers, were prepared by emulsifier‐free emulsion polymerization of poly(n‐butyl acrylate/methyl methacrylate)/polystyrene [P(n‐BA/MMA)/PS]. The particle diameter was about 0.22 μm, and the rubbery core was uncrosslinked and lightly crosslinked, respectively. The smaller core–shell structured particle–toughened PS blends were investigated in detail. The dynamic mechanical behavior and observation by scanning electron microscopy of the modified blend system with core–shell structured particles indicated good compatibility between PS and the particles, which is the necessary qualification for an effective toughening modifier. Notched‐impact strength and related mechanical properties were measured for further evaluation of the toughening efficiency. The notched‐impact strength of the toughened PS blends with uncrosslinked particles reached almost sixfold higher than that of the untoughened PS when 15 phr of the core–shell structured particles was added. For the crosslinked particles the toughening effect for PS was not obvious. The toughening mechanism for these smaller particles also is discussed in this article. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1290–1297, 2003  相似文献   

5.
The N‐phenylmaleimide–styrene copolymer (PMS) was prepared and used to improve the brittleness of the cyanate ester resin. PMS was an effective modifier for improving the brittleness of the resin. The morphologies of the modified resins depended on PMS molecular weight and content. The most effective modification of the cyanate ester resin was attained because of the cocontinuous phase structure of the modified resin. Inclusion of 10 wt % PMS (Mw 133,000) led to an 160% increase in the fracture toughness (KIC) for the modified resin with a slight loss of flexural strength and retention of flexural modulus and the glass transition temperature, compared to the values for the unmodified resin. Low water absorptivity of the parent‐cured resin was not deteriorated by modification. The toughening mechanism was discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified cyanate ester resin system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2931–2939, 1999  相似文献   

6.
The morphology and material properties of dicyandiamide (DICY)‐cured epoxy resins modified with acrylic particles consisting of a PBA (polybutyl acrylate) core and a PMMA (polymethyl methacrylate) shell and epoxy resins modified with acrylic rubber (PBA) particles alone were studied. It was found that the epoxy system modified with core/shell acrylic particles showed higher fracture toughness, indicating that the modification had a larger effect on improving the material properties of the epoxy resin. A characteristic shown by the core/shell acrylic particles is that they swell along with the epoxy resin under exposure to heat and gel before the latter cures. In this process, the epoxy resin penetrates the surface of the shell layer and a bond is formed between the epoxy matrix and the core/shell acrylic particles. This suggests that the epoxy matrix around the core/shell acrylic particles has the effect of increasing the level of energy absorption due to plastic deformation of the matrix. This is thought to explain why the epoxy resin modified with core/shell acrylic particles showed higher fracture toughness. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2955–2962, 1999  相似文献   

7.
N‐Phenylmaleimide–N‐(p‐hydroxy)phenylmaleimide–styrene terpolymer (HPMS), carrying reactive p‐hydroxyphenyl groups, was prepared and used to improve the toughness of cyanate ester resins. Hybrid modifiers composed of N‐phenylmaleimide–styrene copolymer (PMS) and HPMS were also examined for further improvement in toughness. Balanced properties of the modified resins were obtained by using the hybrid modifiers. The morphology of the modified resins depends on HPMS structure, molecular weight and content, and hybrid modifier compositions. The most effective modification of the cyanate ester resin was attained because of the co‐continuous phase structure of the modified resin. Inclusion of the modifier composed of 10 wt% PMS (Mw 136 000 g mol?1) and 2.5 wt% HPMS (hydroxyphenyl unit 3 mol%, Mw 15 500 g mol?1) led to 135% increase in the fracture toughness (KIC) for the modified resin with a slight loss of flexural strength and retention of flexural modulus and glass transition temperature, compared with the values for the unmodified resin. Furthermore, the effect of the curing conditions on the mechanical and thermal properties of the modified resins was examined. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviour of the modified cyanate ester resin system. © 2001 Society of Chemical Industry  相似文献   

8.
A two-stage, multistep soapless emulsion polymerization was employed to prepare various sizes of reactive core–shell particles (CSPs) with butyl acrylate (BA) as the core and methyl methacrylate (MMA) copolymerizing with various concentrations of glycidyl methacrylate (GMA) as the shell. Ethylene glycol dimethacrylate (EGDMA) was used to crosslink either the core or shell. The number of epoxy groups in a particle of the prepared CSP measured by chemical titration was close to the calculated value based on the assumption that the added GMA participated in the entire polymerization unless it was higher than 29 mol %. Similar results were also found for their solid-state 13C-NMR spectroscopy. The MMA/GMA copolymerized and EGDMA-crosslinked shell of the CSP had a maximum glass transition temperature (Tg) of 140°C, which was decreased with the content of GMA at a rate of −1°C/mol %. However, the shell without crosslinking had a maximum Tg of 127°C, which decreased at a rate of −0.83°C/mol %. The Tg of the interphasial region between the core and shell was 65°C, which was invariant with the design variables. The Tg of the BA core was −43°C, but it could be increased to −35°C by crosslinking with EGDMA. The Tg values of the core and shell were also invariant with the size of the CSP. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2069–2078, 1998  相似文献   

9.
Physical and gas transport properties of hyperbranched polyimide (HBPI)—silica hybrid membranes prepared with a dianhydride monomer, 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), and triamine monomers, 1,3,5‐tris(4‐aminophenoxy)triazine (TAPOTZ), and 1,3,5‐tris(4‐aminophenyl)benzene (TAPB), were investigated and compared with those of 6FDA‐TAPOB HBPI system synthesized from 6FDA and 1,3,5‐tris(4‐aminophenoxy)benzene (TAPOB). Glass transition and 5% weight‐loss temperatures of the 6FDA‐based HBPI–silica hybrid membranes were increased with increasing silica content. 6FDA‐TAPOTZ HBPI system, however, showed relatively low 5% weight‐loss temperatures, suggesting thermal instability of triazine‐ring in the TAPOTZ moiety. CO2/CH4 permselectivity of the HBPI–silica hybrid membranes were increased with increasing silica content, tending to exceed the upper bound for CO2/CH4 separation. This result indicated that free volume elements effective for CO2/CH4 separation were created by the incorporation of silica for the HBPI–silica hybrid systems. Especially, 6FDA‐TAPB HBPI system had high gas permeabilities and CO2/CH4 separation ability, arising from high fractional free volume and characteristic size and distribution of free volume elements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

10.
Powder coating is an established technology especially for the surface finishing of metallic substrates for example in the automotive industry. Moreover, powder technology holds also great promises for the coating of non-conventional substrates like plastics or wood due to the lack of solvents and good recoverability. Here, low-temperature curing resins are required and especially mild processing conditions are demanded by the substrates. Advanced characterization methods need to be established that allow the precise balancing of the processing conditions required for adequate melting, flowing and curing of the powder with the process conditions that can be tolerated by the temperature-sensitive substrates. In the present contribution it is shown that differential scanning calorimetry (DSC) in combination with isoconversional kinetic analysis (ICKA) provides great potential for this purpose. DSC is a standard thermo-chemical method that can be successfully used to study both the melting and curing processes of powder coatings and to determine, for example the glass transition temperature of the cured coating directly from the measured thermograms. However, still more information can be extracted from the enthalpy signals when more sophisticated methods of data post-treatment and analysis are employed. Isoconversional kinetic analysis techniques such as the Kissinger–Akahira–Sunose (KAS) or the advanced Vyazovkin (VA) approaches allow calculating the time-dependencies of physical and chemical processes at various temperatures based on the estimates of activation energies which are obtained from DSC raw data. These analyses allow for example to calculate the time required for a certain degree of cross-linking in the coating after processing the coating under specified curing conditions. In the present contribution the application of ICKA of DSC measurements for the analysis of the flowing and curing behaviour of a powder coating based on a polyester–epoxy hybrid resin is illustrated and the potential of this approach to predict optimal curing times for arbitrary curing temperatures is demonstrated. This is especially useful when temperature-sensitive substrates like wood-based panels are coated. Additionally, the potential to relate the thermo-chemical properties of the powder coating to the surface properties of the coated substrates is discussed.  相似文献   

11.
N-Phenylmaleimide–styrene copolymers (PMS) and reactive N-phenylmaleimide–styrene–p-hydroxystyrene (HSt) terpolymers (PMSH) containing p-hydroxyphenyl groups were used to improve the toughness of bisphenol A diglycidyl ether epoxy resin cured with methyl hexahydrophthalic anhydride. PMS and PMSH were effective modifiers for epoxies. The morphologies of the modified resins depended on modifier structure and content. The most effective modification for the cured resins was attained because of the co-continuous structure of the modified resins in both PMS and PMSH modification systems. When using 15wt% of PMS (M¯w 125000), the fracture toughness, KIC, for the modified resin increased by 230%, with retention of flexural modulus and glass transition temperature, but with a loss of flexural strength, compared with the values for the unmodified epoxy resin. When using PMSH as the reactive modifier, the efficiency decreased with increase in HSt content, because of the increasing extent of dispersion of the PMSH-rich continuous phases. In the modification with 10wt% PMSH (1·0mol% HSt unit, M¯w 294000), the modified resin had balanced physical properties. © of SCI.  相似文献   

12.
The surface modification of sulfur‐prevulcanized natural rubber (SPNR) sheets by the polyethyleneimine‐functionalized‐poly(methyl methacrylate) (PMMA/PEI) nanoparticles was successfully performed via a simple dipping method. The percentage of surface coverage (Cs) of the nanoparticles on SPNR sheets was found to be affected by a variation of nanoparticle latex concentrations and immersion times. The adsorption isotherm of PMMA/PEI nanoparticles on SPNR sheets was analyzed and found to fit well to the Freundlich model. After coating, it can be observed that the presence of PMMA/PEI nanoparticles on SPNR surface had no effects over the SPNR mechanical properties e.g., tensile strength, elongation at break, and hardness. On the other hand, the coated SPNR sheets showed a reduction of surface friction coefficients and interfacial adhesion up to 45 and 59%, respectively. Furthermore, PMMA/PEI nanoparticles adsorbed on the SPNR surface was subjected to stretching and wearing conditions, and found to be stable for at least seven stretching and wearing cycles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

13.
Background: Poly(ethylene terephthalate) (PET)/polyamide‐6 (PA‐6) blends are promising for engineering and food‐packaging applications. However, their poor toughness limits their use. In this study, an ethylene–acrylate–(maleic anhydride) terpolymer (E‐AE‐MA) was added to PET/PA‐6 blends in order to improve the toughness. Results: Izod impact tests indicated an excellent toughening effect of E‐AE‐MA. E‐AE‐MA particles were observed to be selectively dispersed at the interface between PET and PA‐6 phases and in the domain of the PA‐6 phase. Fourier transform infrared spectroscopy and differential scanning calorimetry results demonstrated that the formation of E‐AE‐MA layers around PA‐6 particles cut off the interaction between PET and PA‐6, resulting in an enlarged PA‐6 phase domain. Conclusion: Based on the experimental results, a core–shell microstructure, with PA‐6 as a hard core and E‐AE‐MA as a soft shell, could be suggested. The formation of this core–shell microstructure, along with the increased PA‐6 phase domain size, is the main toughening mechanism of E‐AE‐MA in PET/PA‐6 blends. Copyright © 2007 Society of Chemical Industry  相似文献   

14.
Mechanical properties and fracture mechanisms of Novatein thermoplastic protein and blends with core–shell particles (CSPs) have been examined. Novatein is brittle with low impact strength and energy‐to‐break. Epoxy‐modified CSPs increase notched and unnotched impact strength, tensile strain‐at‐break, and energy‐to‐break, while tensile strength and modulus decrease as CSP content increases. Tg increases slightly with increasing CSP content attributed to physical crosslinking. Changes to mechanical properties are related to the critical matrix ligament thickness and rate of loading. Novatein control samples display brittle fracture characterized by large‐scale crazing. At high CSP content a large plastic zone and a slow crack propagation zone in unnotched and tensile samples are observed suggesting increased energy absorption. Notched impact samples reach critical craze stresses easily regardless of CSP content reducing impact strength. It is concluded that the impact strength of thermoplastic protein can be modified in a similar manner to traditional thermoplastics.

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15.
The transparent hybrid material, HLP/SiO2, was prepared by an in situ sol–gel process of tetraethoxysilane (TEOS) at 30°C in the presence of hydroxy‐containing linear polyester (HLP) obtained by ring‐opening reaction of diglycidyl ether of bisphenol A (DGEBA) with adipic acid under the catalyzation of triphenylphosphine (TPP). The hetero‐associated hydrogen bonds between the HLP and the residual silanol of silica in the hybrids were investigated by FTIR spectroscopy. Upon heating the hybrid, the interfacial force between the HLP matrix and the silica network changed from hydrogen bonds into covalent Si—O—C bonds through dehydration of hydroxy groups in HLP with residual silanol groups in the silica network. The existence of covalent Si—O—C bonds was proved by solid‐state 29Si‐NMR spectra. Other properties such as tensile strength, glass transition temperature (Tg ), solubility, and thermal stability of the hybrids before and after heat treatment were studied in detail. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1179–1190, 2000  相似文献   

16.
The sol–gel process has been frequently employed for preparation of high performance silica/polymer composites. In this paper, novel sol–gel precursor triethoxysilane‐terminated poly(urethane‐imide) (PUI‐Si), combining the advantages of polyurethane (PU) and polyimide, was synthesized and characterized. Then PUI‐Si was incorporated into the epoxy resin matrix to prepare a series of EP/PUI‐Si organic‐inorganic hybrids through an in situ sol–gel process and crosslinking reactions. The thermal stability of EP/PUI‐Si hybrids was evaluated by thermogravimetric analysis and the results show that the PUI‐Si could significantly improve the thermal properties of epoxy resin. The initial decomposition temperature of composites with 50 wt% PUI‐Si reached 347.1 °C, 157.3 °C higher than that of neat epoxy resin. Furthermore, the tensile strength and breaking elongation can also be clearly improved by adding a suitable amount of PUI‐Si. Similarly, the water contact angle increased to 97.4° with 70 wt% PUI‐Si, showing a hydrophobic surface. The morphology was investigated by transmission electron microscopy and the results reveal that the silica particles are smaller than 20 nm and have a strong interaction with the epoxy resin matrix, resulting in the above‐mentioned high performance properties. Copyright © 2011 Society of Chemical Industry  相似文献   

17.
BACKGROUND: Hollow microspheres, especially biodegradable polymeric microspheres, have attracted considerable attention due to their particular characteristics. Up to now, microspheres have been prepared via various strategies, for instance the template synthesis method and the self‐assembly process. However, economic, novel and simple methods to prepare hollow microspheres are still being sought. RESULTS: Phosphazene‐containing microspheres, which contain self‐assembled core‐shell structures, were prepared at high colloid contents using an ultrasonic bath via a self‐template approach. Along with the controlled self‐degradation of the internal core, the corresponding hybrid inorganic–organic hollow microspheres appeared. The mechanism was evidenced by means of transmission and scanning electron microscopy, cross‐polarization with magic angle spinning NMR, Fourier transform infrared spectroscopy, X‐ray diffraction and thermogravimetric analysis. CONCLUSION: It was clarified that the phosphazene‐containing microspheres could be formed and stably dispersed without aggregation even at high colloid contents using the ultrasonic bath method and the microspheres contain self‐assembled core–shell structures. Along with the controlled self‐degradation of the internal core, the corresponding hollow microspheres appeared. The mechanism of this preparation is of great significance because it is completely different from the conventional template synthesis method and the self‐assembly process. The absence of any stabilizing agent and special templates might inspire creative imagination in the design of new morphologies of micro‐ and nanostructures. Copyright © 2007 Society of Chemical Industry  相似文献   

18.
Core–shell poly(acrylic acid)/polystyrene/SiO2 (PAA/PS/SiO2) hybrid microspheres were prepared by dispersion polymerization with three stages in ethanol and ethyl acetate mixture medium. Using vinyltriethoxysilane (VTEOS) as silane agent, functional silica particles structured vinyl groups on surfaces were prepared by hydrolysis and polycondensation of tetraethoxysilane and VTEOS in core stage. Then, the silica particles were used as seeds to copolymerize with styrene and acrylic acid sequentially in shell stage I and stage II to form PAA/PS/SiO2 hybrid microspheres. Transmission electron microscope results show that most PAA/PS/SiO2 hybrid microspheres are about 40 nm in diameter, and the silica cores are about 15 nm in diameter, which covered with a layer of PS about 7.5‐nm thick and a layer of PAA about 5‐nm thick. This core–shell structure is also conformed by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and differential scanning calorimetry. FTIR results show that silica core, PS shell, and PAA outermost shell are bonded by covalents. In the core–shell PAA/PS/SiO2 hybrid microsphere, the silica core is rigidity, and the PAA outermost shell is polarity, while the PS layer may work as lubricant owning to its superior processing rheological property in polymer blending. These core–shell PAA/PS/SiO2 hybrid microspheres have potential as new materials for polar polymer modification. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1729–1733, 2006  相似文献   

19.
Polymer–inorganic hybrid nanoparticles were prepared through radical photo‐polymerization of methyl methacrylate initiated by N,N‐diethyldithiocarbamyl surface functionalized silica nanoparticles under UV irradiation at ambient temperature. IR analysis and UV spectroscopy confirmed the occurrence of Et2NCS2—end groups on the resulting poly(methyl methacrylate), and the morphology of these hybrid nanoparticles was observed directly by means of tapping mode atomic force microscopy (AFM). Copyright © 2003 Society of Chemical Industry  相似文献   

20.
A study of hygrothermal aging in terms of the kinetics of moisture absorption by poly(butylene terephthalate) (PBT) and styrene‐acrylonitrile/acrylate based core–shell rubber (CSR) toughened PBT (PBT‐CSR) was undertaken. The diffusion of water into the PBT compounds with various CSR contents was investigated by immersion of specimens in water at temperatures between 30 and 90°C. It was observed that the equilibrium moisture content and the diffusion coefficient of the PBT both increased with increasing CSR content. The fracture behaviors of the PBT and PBT‐CSR were investigated. The focus of investigation was on the effect of an internal parameter (rubber content) and external parameters (testing temperature, deformation rates, and hygrothermal aging) on the fracture behavior of these materials. The fracture response of the various materials was evaluated by the fracture toughness and energy measured on static‐loaded compact tension specimens. The tensile and fracture behavior of PBT and PBT‐CSR was affected by both the internal and external parameters. On its own the CSR impact modifier failed to improve the toughness of PBT at either high testing speed or subambient temperature (−40°C). Based on the dynamic mechanical analysis study, the CSR is believed to behave as a rigid particulate filler in the PBT that consequently reduces the ductility of the PBT. All the materials tested showed poor retention of the tensile and fracture properties upon exposure to hygrothermal aging at 90°C, and these properties could not be restored by subsequent drying. This was attributed to severe hydrolytic degradation of the PBT that caused permanent damage to the materials. The failure modes of PBT and PBT‐CSR were assessed by fractographic studies in a scanning electron microscope. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2470–2481, 1999  相似文献   

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