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A method for determining respectively the concentration of free radicials...CF2-CF2.(RI), ...CF2-CF-CF2...(RII)and...CF2- C(CF3)-CF2...(RIII) trapped in γ-irradiated F46 in vacuum at room temperature by analysing the ESR overlapping spectra is proposed. A quantitative relation between the concentration of free readicals and the total dose of γ-irradiation has been studied. The generating rate o free radicals caused by irradiation, i.e. G-value, has been calculated; it is 2.0 for RIII, 1.2 for RI, and 0.59 for RII. the magnitude of G value of free radicals is in the reverse order of their stability. Hence, we assume that the G value of free radicals in F46 mainly depends on the escaping rate of F2 and other fluorine-containing small molecules from surface of polymer into space. Therefore the looser the molecular chain, the larger becomes the G value of free radical. From that, we consider that both unstable free radicals RIII and RI with larger G-value mainly locate in the amorphous region, and the stable free radical RII with lower G-value is in the crystalline region. Recombinations between free radicals RII and RIII, or between RII and RI are forbidden at the temperature lower than 80C. An explanation for the saturation phenomenon of concentration of free radicals is given. 相似文献
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An aromatic diamine monomer,4,4'-bis(3-amino-5-trifluoromethyl phenoxy)-biphenyl (TFBPDA),wassynthesized via the nucleophilic displacement reaction of 3,5-dinitrobenzotrifluoride and 4,4'-biphenol.The monomer wasreacted with various aromatic dianhydrides via the high temperature polycondensation procedure to provide a series ofpolyimides.The polyimides,PI-1 to PI-4,show good solubility not only in aprotic solvents,such as N-methyl-2-pyrrolidinone and N,N-dimethylacetamide,but also in many common solvents,such as m-cresol,chloroform andcyclopentanone.PI-4,derived from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and TFBPDA,was even soluble intoluene.Moreover,PI films exhibit good thermal stability,outstanding transparency in the visible light region and acceptablemechanical and electrical properties.The excellent combined properties of the polyimides make them as a good candidate forfabricating microelectronics. 相似文献
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Autooxidation processes of free radicals trapped in γ irradiated F46 copolymer in vacuum at room temperature were studied by means of ESR. It is shown that these processes are under the dual control of both the diffusion of oxygen and the total concentration of free radicals, and they are independent of the autooxidation reaction rate constant. In general, the diffusion constant calculated by simple diffusion equation is an apparent diffusion constant, it is a function of the total concentration of free radicals. Only when the total concentration of free radicals is low enough (in our case n-2X10^1^7 spins/g), the apparent diffusion constant is close to its real value on unirradiated sample. By the method given in this paper, the diffusion constant of oxygen has been calculated to be 1.6X10^-^7 cm^2/sec at 20`C for F46 film obtained by suspension polymerization. 相似文献
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A novel unsymmetrical fluorinated diamine monomer with kink non-coplanar heterocyclic structures, 1,2-dihydro- 2-(4-amino-2-trifluoromethyophenyo)-4-[4-(4-amino-2-trifluoromethyophenoxy)phenyo](2H)phthaoazin-1-oneo was prepared through the nucleophilic substitution reaction of 1-trifluromethyl-2-chloro-5-nitrobenzene with 1,2-dihydro-4-(4- hydroxyphenyl)(2H)phthalazin-l-one in the presence of potassium carbonate, followed by catalytic reduction with hydrazine and Pd-C. A series of new fluorinated polyarnides were synthesized by the phosphorylation polyamidation of the fluorinated diamine with various dicarboxylic acids. The prepared polymers were obtained in quantitative yields with moderately and high inherent viscosities (0.47-0.87 dL/g). They were all amorphous and readily soluble in various polar aprotic solvents such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacctamide (DMAc), pyridine (Py) and m-cresol at room temperature. These fluorinated polyamides have excellent thermal properties. The glass transition temperatures were all above 300℃. The 5% and 10% weight loss temperatures were in the range of 437-466℃ and 482-525℃ in nitrogen atmosphere, respectively. 相似文献
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HongTan MinGuo Jie-huaLi Xing-yiXie Yin-pingZhong QiangFu 《高分子科学》2004,(3):299-303
The surface phase separated structure of polyurethanes is always desired due to the advantage of better biocompatibility, compared with the homogeneous one. The key issue is how to control and characterize the surface morphology. In this work, we report the uppermost surface morphology of fluorinated poly(carbonate urethane)s with fluorinated side chains attached to hard segments as studied by AFM, XPS and contact angle measurement. A self-assembled micro-domain with the fluorinated side chain standing up on the uppermost surface has been proposed for polyurethane with higher fluorinated content, based on the result obtained 相似文献
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A series of copolymers comprising butylmethacrylate, styrene, butylacrylate, hydroxypropyl acrylate and perfluoroalkyl methacrylate were synthesized by the free radical polymerization using BPO as an initiator. The surface property of the copolymer films was subsequently characterized. The contact angle measurements and energy dispersive analysis of X-ray (EDAX) show that the length and content of perfluoroalkyl side chains in the copolymers are crucial for the preparation of the film with low surface energy. At a given content of fluorinated monomers in the copolymers, the longer the perfluoroalkyl side chain, the larger the water contact angle of the copolymer films will be. On the other hand, the higher the content of fluorinated monomers, the lower the surface energy is. The water contact angle increases with the increase of the fluorinated monomer content and reaches a plateau at 3 wt% of fluorinated monomer content. 相似文献
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