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1.
A series of fluorine‐containing bismaleimide (FBMI) monomers are synthesized by a 3‐step reaction for using as the applications of low‐k materials. The synthesized FBMI monomers are characterized by the 1H, 13C, 19F nuclear magnetic resonance (NMR) spectroscopy and element analysis. These FBMI monomers react with free radical initiator or self‐cure to prepare FBMI‐polymers. All the self‐curing FBMI resins have the glass transition temperatures (Tg) in the range of 128–141°C and show the 5% weight loss temperatures (T5%) of 235–293°C in nitrogen atmosphere. The higher heat resistance of self‐curing FBMI resin relative to FBMI‐homopolymer is due to its higher crosslinking density. The FBMI resins exhibit improved dielectric properties as compared with commercial bismaleimide (BMI) resins with the dielectric constants (Dk) lower than 2.49, which is related to the low polarizability of the C? F bond and the large free volume of CF3 groups in the polymers. Besides, the flame retardancy of all these FBMI resins could be enhanced via the introduction of Br‐atom. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

2.
A novel energetic polymer, fluorine‐containing glycidyl azide polymer (FGAP ), was developed via an initial cationic copolymerization of epichlorohydrin and 1,1,1‐trifluoro‐2,3‐epoxypropane, followed by azidation. The structure of FGAP was confirmed using Fourier transform infrared, 1H NMR and 13C NMR spectroscopies. The molecular weight and the thermal behavior of FGAP were characterized using gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. FGAP had a molecular weight of 2845 g mol?1, and the glass transition temperature and decomposition temperature were found to be ?47.8 and 253 °C, respectively. FGAP ‐based polyurethane networks were further prepared using triphenylmethane‐4,4,4‐triisocyanate as the crosslinking agent. In comparison with GAP , FGAP ‐based polyurethane networks exhibited better mechanical behaviors (a tensile strength of 1.5 MPa and an elongation at break of 81.6%). The results demonstrated that FGAP might be a promising polymeric binder for future propellant formulations. © 2017 Society of Chemical Industry  相似文献   

3.
A series of fluorine‐containing copolyimides were synthesized by three different orders of addition of monomers. The fluorine‐containing copolyimides were prepared by the reaction of 4,4′‐diaminodiphenylmethane (DDM) with 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), and pyromellitic dianhydride (PMDA). The synthesis reactions of the copoly(amic acid)s (PA) were carried out by three different orders of addition of the monomers with different molar ratios of 6FDA to PMDA. The viscosity of the PA solution obtained by DDM–(6FDA+PMDA), that is, 6FDA and PMDA added simultaneously to DDM in N‐methyl‐2‐pyrrolidinone (NMP), was higher than the other two addition orders (i.e., DDM–6FDA–PMDA and DDM–PMDA–6FDA). The viscosity decreased as the relative amount of 6FDA to PMDA increased. The copolyimides formed by different addition orders but the same 6FDA‐to‐PMDA molar ratios contained different properties, such as dielectric constant, moisture absorption, contact angle, and optical transparency. All of these copolyimides were insoluble in common organic solvents, such as NMP and tetrahydrofuran. Thermogravimetric analysis showed that the onset temperature of 8% weight loss decreased slightly as [6FDA] : [PMDA] increased. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3252–3258, 2000  相似文献   

4.
Fluorine‐containing poly[bis‐(2,2,3,3,4,4,5,5‐octafluoro‐1‐pentanol)1.6 (4‐hydroxybutaneoxy)0.4 phosphazene] (OFHBP) was synthesized and characterized by Fourier transform infrared (FTIR) spectra, nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC). The obtained OFHBP was used as a cross‐linker to prepare a series of novel polyurethanes (PUPFs). The composition of the PUPFs was confirmed by FTIR and elemental analysis (EA). The crystalline structure and microstructure of the PUPFs were examined by X‐ray diffraction (XRD) and atomic force microscopy (AFM). The thermal and tensile properties of the PUPFs were characterized by differential scanning calorimetry (DSC) and tensile testing. In addition, the surface energy of the PUPFs was also evaluated by contact angle measurements (CA). The results showed that glass transition temperature of the PUPF‐4 was decreased by 15°C, elongation at break was improved by 61% and a 41% decrease in surface energy in comparison with conventional polyurethane. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

5.
A novel siloxane‐imide‐containing polybenzoxazine based on N,N′‐bis(N‐phenyl‐3,4‐dihydro‐2H‐benzo[1,3]oxazine)‐5, 5′‐bis(1,1′,3,3′‐tetramethyldisiloxane‐1,3‐diyl)‐bis(norborane‐2,3‐dicarboximide) (BZ‐A1) was successfully synthesized. The thermal properties of BZ‐A1 are superior to those of conventional polybenzoxazines lacking siloxane groups. Polymerized BZ‐A1 possesses extremely low surface free energy (γs = 15.1 mJ m?2) after curing at 230 °C for 1 h. Moreover, the surface free energy of polymerized BZ‐A1 is more stable than conventional bisphenol A‐type polybenzoxazine during thermal curing and annealing processes, indicating that polymerized BZ‐A1 is more suitable for applications requiring low surface free energy materials for high temperatures over long periods of time. Copyright © 2010 Society of Chemical Industry  相似文献   

6.
BACKGROUND: ABA‐type poly(methyl methacrylate) (PMMA) and fluorine‐containing polyimide triblock copolymers are potentially beneficial for electric materials. In the work reported here, triblock copolymers with various block lengths were prepared from fluorine‐containing difunctional polyimide macroinitiators and methyl methacrylate monomer through atom‐transfer radical polymerization. The effects of structure on their solid and thermal properties were studied. RESULTS: The weight ratios of the triblock copolymers derived using thermogravimetric analysis were shown to be almost identical to the ratios determined using 1H NMR. The solid properties (film density and maximum d‐spacing value) and thermal properties (glass transition and thermal expansion) were shown to be strongly dependent on the weight ratios of both PMMA and polyimide components. Furthermore, a porous film, which showed a lower dielectric constant of 2.48 at 1 MHz, could be prepared by heating a triblock copolymer film to induce the thermal degradation of the PMMA component. CONCLUSION: The use of the polyimide macroinitiator was useful in the preparation of ABA‐type triblock copolymers to control each block length that influences the solid and thermal properties. Additionally, the triblock copolymers have great potential in preparing porous polyimides in the application of electric materials as interlayer insulation membranes of large‐scale integration. Copyright © 2009 Society of Chemical Industry  相似文献   

7.
We report a facile strategy for fabricating fluorescent quantum dot (QD)‐loaded microbeads by means of microfluidic technology. First, a functional fluorine‐containing microemulsion was synthesized with poly[(2‐(N‐ethylperfluorobutanesulfonamido)ethyl acrylate)‐co‐(methyl methacrylate)‐co‐(butyl acrylate)] (poly(FBMA‐co‐MMA‐co‐BA)) as the core and glycidyl methacrylate (GMA) as the shell via differential microemulsion polymerization. Then, CdTe QDs capped with N‐acetyl‐l ‐cysteine (NAC) were assembled into the poly(FBMA‐co‐MMA‐co‐BA‐co‐GMA) microemulsion particles through the reaction of the epoxy group on the shell of the microemulsion and the carboxyl group of the NAC ligand capped on the QDs. Finally, fluorescent microbeads were fabricated using the CdTe QD‐loaded fluorine‐containing microemulsion as the discontinuous phase and methylsilicone oil as the continuous phase by means of a simple microfluidic device. By changing flow rate of methylsilicone oil and hybrid microemulsion system, fluorescent microbeads with adjustable sizes ranging from 290 to 420 µm were achieved. The morphology and fluorescent properties of the microbeads were thoroughly investigated using optical microscopy and fluorescence microscopy. Results showed that the fluorescent microbeads exhibited uniform size distribution and excellent fluorescence performance. © 2014 Society of Chemical Industry  相似文献   

8.
A new synthetic route was designed to significantly increase the content of triazine structure in benzoxazine resin. 2,4,6‐Tri(4‐hydroxylphenyl)‐13,5‐s‐triazine (TP) was synthesized by cyclotrimerization of 4‐cyanolphenol and then benzoxazine monomer‐containing triazine [2,4,6‐tri(3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazin‐6‐yl)‐1,3,5‐s‐triazine (BZ‐ta)] was synthesized via Mannich reaction from TP. Finally, the cross‐linked polymer P(BZ‐ta) was produced by thermal polymerization of BZ‐ta. BZ‐ta was characterized by nuclear magnetic resonance spectroscopy (NMR), fourier transform infrared spectroscopy (FTIR), mass spectrum, elemental analysis, and viscosity measurement. Curing behavior of BZ‐ta was studied by differential scanning calorimetry, FTIR, and gel permeation chromatography. The structure and properties of P(BZ‐ta) were investigated by powder X‐ray diffraction, dynamic mechanical analysis, and thermogravimetric analysis. The results showed that the P(BZ‐ta) had high glass temperature (Tg = 322°C), excellent thermal oxidation stability (5 and 10% weight loss temperatures in air up to 403 and 453°C, respectively), high char yield (64%, 800°C in nitrogen), and high flame‐retardance (limiting oxygen index, 39.7). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

9.
A new kind of pyridine‐containing aromatic diamine monomer, 4‐phenyl‐2,6‐bis[4‐(4‐aminophenoxy)phenyl]‐pyridine (PAPP), was successfully synthesized by a modified chichibabin reaction of benzaldehyde and a substituted acetophenone, 4‐(4‐nitrophenoxy)‐acetophenone (NPAP), followed by a reduction of the resulting dinitro compound 4‐phenyl‐2,6‐bis[4‐(4‐nitrophenoxy)phenyl]‐pyridine (PNPP) with Pd/C and hydrazine monohydrate. The aromatic diamine was employed to synthesize a series of new pyridine‐containing polyimides by polycondensation with various aromatic dianhydrides in N‐methy‐2‐pyrrolidone (NMP) via the conventional two‐step method, i.e., ring‐opening polycondensation forming the poly (amic acid)s and further thermal or chemical imidization forming polyimides. The inherent viscosities of the resulting polyimides were in the range of 0.79–1.13 dL/g, and most of them were soluble in common organic solvents such as N,N‐dimethylacetamide (DMAc), NMP, and tetrahydrofuran (THF), etc. Meanwhile, strong and flexible polyimide films were obtained, which had good thermal stability, with the glass transition temperatures (Tg) of 268–338°C and the temperature at 5% weight loss of 521–548°C in air atmosphere, as well as outstanding mechanical properties with tensile strengths of 89.2–112.1 MPa and elongations at break of 9.5–15.4%. The polyimides also were found to possess low dielectric constants ranging from 2.53 to 3.11. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 212–219, 2007  相似文献   

10.
Three novel kinds of linear silicon‐containing hybrid polymers with Si?C≡C units were synthesized by polycondensation reactions using the Grignard reagent method. All the polymers were thermosetting, highly heat‐resistant, moldable and easily soluble in common organic solvents. The structure, curing behavior, thermal and oxidative properties were characterized using Fourier transform infrared spectroscopy, 1H NMR, 13C NMR, gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. The results obtained can provide theoretical guidance for determining the curing of the resin system. In addition, the cured polymers exhibit excellent thermal and oxidative stabilities with temperatures of 5% weight loss (Td5) above 480 °C and 450 °C in nitrogen and air respectively; the residues at 1000 °C were above 70.0% and 45.0% respectively. The thermal and oxidative stabilities of the polymers are attributed to a crosslinking reaction between the Si?H and C≡C bonds or C≡C bonds. These polymers have the potential for use as high‐temperature‐resistant resins and ceramic precursors. © 2013 Society of Chemical Industry  相似文献   

11.
4,4'‐(Hexafluoroisopropylidene) diphthalic anhydride 2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) polyimide macroinitiator was synthesized and reacted with poly(methyl methacrylate) (PMMA) to form an ABA‐type triblock copolymer by atom transfer radical polymerization. The effect of the ABA‐type triblock copolymer structure on solid, thermal, optical and gas transport properties was systematically investigated and compared with the physical blend polymer. The blend polymer was cloudy, whereas the triblock copolymer was colorless and transparent. The PMMA component decomposition temperature for the triblock copolymer slightly shifted to higher temperature, while its gas barrier property was higher than the blend polymer. The refractive index and the gas permeability decreased while maintaining the heat resistance by a high nanoscale distribution of both polymer components. The 6FDA‐TeMPD/PMMA ABA‐type triblock copolymer can be described as a polymer material with high heat resistance, high gas barrier property and low refractive index amongst existing polymers. © 2013 Society of Chemical Industry  相似文献   

12.
The free‐radical‐initiated copolymerization of 2‐(4‐acetylphenoxy)‐2‐oxoethyl‐2‐methylacrylate (AOEMA) and 2‐(4‐benzoylphenoxy)‐2‐oxoethyl‐2‐methylacrylate (BOEMA) with 2‐[(4‐fluorophenyoxy]‐2‐oxoethyl‐2‐methylacrylate (FPEMA) were carried out in 1,4‐dioxane solution at 65°C using 2,2′‐azobisisobutyronitrile as an initiator with different monomer‐to‐monomer ratios in the feed. The monomers and copolymers were characterized by FTIR and 1H‐ and 13C‐NMR spectral studies. 1H‐NMR analysis was used to determine the molar fractions of AOEMA, BOEMA, and FPEMA in the copolymers. The reactivity ratios of the monomers were determined by the application of Fineman‐Ross and Kelen‐Tudos methods. The analysis of reactivity ratios revealed that BOEMA and AOEMA are less reactive than FPEMA, and copolymers formed are statistically in nature. The molecular weights (M w and M n) and polydispersity index of the polymers were determined using gel permeation chromatography. Thermogravimetric analysis of the polymers reveals that the thermal stability of the copolymers increases with an increase in the mole fraction of FPEMA in the copolymers. Glass transition temperatures of the copolymers were found to decrease with an increase in the mole fraction of FPEMA in the copolymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

13.
A novel fluorine‐containing acrylic resin, 4‐trifluoromethylphenyl glycerol dimethacrylate (TPGD), was synthesized and the structure was characterized by FTIR, 13C NMR, 1H NMR, and 19F NMR spectroscopy. The conversion of cure reaction, thermal stability, glass transition temperature (Tg), and electrical properties of the TPGD acrylic resin cured with UV radiation were investigated. The thermal stability and Tg of the UV‐cured specimens show a maximum value at 1 wt% photoinitiator, due to the formation of advanced network structures. The cured specimens had a relatively low dielectric constant, attributed to the decreased deformation polarizability of segment motion in the fluorine‐containing resin. Copyright © 2004 Society of Chemical Industry  相似文献   

14.
Two types of polybenzoxazine (PBZ) hybrid nanocomposites were prepared from new type of benzoxazine monomer (BZ‐Cy‐OH) and organo‐modified MMT clay (OMMT) and octakis (dimethylsiloxypropylglycidylether) silsesquioxane (OG‐POSS) (up to 7.5 wt%). The new BZ‐Cy‐OH prepared from trans‐4‐aminocyclohexanol hydrochloride and 37% formaldehyde solution with 1,1‐bis (3‐methyl‐4‐hydroxy phenyl) cyclohexane and its structure was conformed by FTIR and NMR (1H and 13C) spectral studies. The thermal properties of the resulting hybrid PBZ nanocomposites were studied by using differential scanning calorimetric and thermogravimetric analysis. Comparative study revealed on the data from the DSC analysis, the newly synthesized BZ‐Cy‐OH started ring opening polymerization at the lower temperature than that of the conventional benzoxazine (Ba‐A). The dispersion of OMMT clay in the PBZ was confirmed by X‐ray diffraction analysis. The homogeneous morphology of the hybrid nanocomposites was studied by using scanning electron microscope and transmission electron microscope analysis. By comparing the dielectric properties of organoclay and POSS filled PBZ nanocomposites, it was observed that the POSS filled PBZ showed low dielectic constant and in the case of organoclay filled PBZ possessed high dielectric constant. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers  相似文献   

15.
Aromatic polyetherimides were synthesized from a fluorine containing aromatic carboxylic acid dianhydride, 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride (6F‐BABPA) and five typical aromatic diamines including 1,1‐bis(4‐aminophenyl)‐1‐phenyl‐2,2,2‐trifluoroethane (3F‐DAM) by two‐step procedures—amidation to polyamic acids (PAA), followed by thermal imidization of PAA. The chemical and physical properties of the newly prepared polyetherimides (PEI) were compared in terms of their chemical structures, inherent viscosities, mechanical, and thermal properties. All polyetherimides were well soluble in common organic solvents such as N‐methyl‐2‐pyrolidone (NMP), N,N‐dimethylformamide (DMF), N,N‐dimethylacetamide (DMAc), pyridine, and methylene chloride. A PEI prepared from 6F‐BABPA/3F‐DAM was especially easily dissolved in NMP. The glass transition temperature (Tg) range of the obtained PEI was 209–257°C. The dielectric constants and refractive index were 2.8–3.2 and 1.61–1.56, respectively. The polyetherimide, 6F‐BABPA/BAPP, with a low fluorine content (11.4% fluorine content), has 0.99% water absorption, whereas the polyetherimide, 6F‐BABPA/4‐BDAP, having a high fluorine content (26.0% fluorine content) showed 0.35% of water absorption. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 249–257, 2000  相似文献   

16.
Phenolic foam exhibits outstanding flame, smoke and toxicity properties, good insulation properties and low production costs. However, the brittleness and pulverization of phenolic foam have severely limited its application in many fields. In this study, a novel phosphorus‐containing polyurethane prepolymer (DOPU) modifier was firstly synthesized, and then the foaming formula and processing of toughening phenolic foam modified with DOPU and glass fiber were explored. The structure and reactive behavior of prepolymer and phenolic resin were investigated using Fourier transform infrared spectroscopy. The effects of DOPU and glass fiber on the apparent density, compressive strength, bending strength and water absorption were investigated. The results suggested that the apparent density, compressive strength and bending strength of modified phenolic foam tended to increase irregularly with increasing content of DOPU. The addition of DOPU led to lower water absorption of glass fiber‐filled foam. Thermal stability and flame retardancy were examined using thermogravimetric analysis and limiting oxygen index (LOI) tests. It was found that foam with 3% DOPU and 0.5% glass fiber added exhibited good thermal stability and high char yields. The LOI value of modified phenolic foams decreased with increasing DOPU content, but it still remained at 41.0% even if the amount of modifier loaded was 10 wt%. © 2012 Society of Chemical Industry  相似文献   

17.
ABA‐type triblock copolymers derived from 4,4'‐(hexafluoroisopropylidene)diphthalicanhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) and methacryl phenyl polyhedral oligomeric silsesquioxane (MPPOSS) were synthesized by atom transfer radical polymerization. The chemical structure of the synthesized ABA‐type triblock copolymer was confirmed by 1H NMR, 13C NMR, 29Si NMR and Fourier transform infrared analyses. The ratios of 6FDA‐TeMPD and MPPOSS determined by TGA were 94/6, 85/15, 77/23, 68/32, 57/43 and 31/69. The film density of the ABA‐type triblock copolymer films did not conform to the mixing rule because of polyimide (PI) chain aggregation. Based on contact angle and water uptake analyses, the hydrophobicity of the ABA‐type triblock copolymer film was determined to be higher than the theoretical value because of POSS cage effects and PI chain aggregation. The gas permeability coefficient of the ABA‐type triblock copolymer decreased compared with that of PI because of aggregation of PI chains and inhibition of solubility decreases by substitutes with high affinity. ABA‐type triblock copolymer CO2/H2 separation performance increased compared with that of PI. The ABA‐type triblock copolymer derived from PI and MPPOSS can be described as a polymer material with higher hydrophobicity and higher CO2/H2 selectivity than PI. © 2015 Society of Chemical Industry  相似文献   

18.
A novel 2‐oxazoline‐benzoxazine (POB) was synthesized with 2‐(hydroxylphenyl)‐2‐oxazoline, 1,3,5‐triphenylhexahydro‐1,3,5‐triazine and paraformaldehyde. The chemical structure of the monomer was confirmed by FTIR, 1H‐NMR, 13C‐NMR, and MS. The curing behavior of the monomer was studied by DSC and FTIR, and the ring opening reaction of the monomer was found to occur from 187.5°C. The results of DMA and TGA demonstrated that the thermal properties of polymer for POB monomer (P‐m) are better than polymer for POB precursor (P‐p), because that the oligomer in benzoxazine precursor decreased the perfection of the polymer's network structure; it was also found that the thermal properties of P‐m and P‐p are much better than the common polybenzoxazine and the composite material of benzoxazine and 2‐oxazoline. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci , 2008.  相似文献   

19.
In this article, a new method to synthesize novel metaloquinolate (AlQ3, ZnQ2)‐containing polymers is reported. A model polymer with 8‐hydroxyquinoline ligands can be obtained by free‐radical copolymerization with methyl methacrylate (MMA), then metaloquinolate (AlQ3, ZnQ2)‐containing polymers are prepared by coordinating reaction with di(8‐hydroxyquinoline) aluminum (AlQ2) chelates or mono (8‐hydroxyquinoline) zinc (ZnQ) chelates without crosslinking. The structures of products are confirmed by NMR, FTIR, ultraviolet‐visible, elementary analysis, photoluminescence spectrum, and gel permeation chromatography analysis. They are soluble in common solvents and suitable to form films. The use of AlQ2 and ZnQ avoided the crosslinking caused by the AlQ3, ZnQ2 formation between different polymer chains. Different from the traditional small organic molecules in organic light‐emitting diodes (OLEDs) fabrication, the polymer can be processed by spin coating without phase separation. Compared to the PMMA or MMA‐co‐HEMA‐CH2‐Hq, the Tg of the metaloquinolate‐containing polymers was much higher. It should be of interest for OLED applications. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1945–1952, 2006  相似文献   

20.
In this work, the pyromellitic dianhydride (PMDA)‐grafted β‐cyclodextrin (β‐CD) microspheres have been prepared for the removal of lead and cadmium metal ions in aqueous solution by a batch‐equilibration technique. The effects of the pH of the solution, contact time, and initial metal concentration were studied. The adsorption capacities for the two metal ions increase significantly as a large number of carboxyl groups are present on the microspheres surface. The equilibrium process is better described by the Langmuir isotherm than the Freundlich isotherm. The maximum adsorption capacities are 135.69 and 92.85 mg g?1 for Pb(II) and Cd(II), respectively. Kinetic studies show good correlation coefficients for a pseudosecond‐order kinetic model, confirming that the sorption rate is controlled by chemical adsorption. The regeneration of the adsorbent can be carried out by treating the loaded microspheres with 0.2 (mol L?1) HCl obtaining high desorption rate for the two metal ions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

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