Fluorinated poly diamine

It reduces the intermolecular CTC between alternating electron donor (diamine) and electron acceptor (dianhydride) moieties. In general, fluorinated poly-imides exhibit lighter color and greater transparency than non-fluorinated analogues [42]. 

Tao et al. prepared fluorinated polyimide (3-86 in Table 3.4) [126], from multi-trifluoromethyl-substituted diamine, which had a dielectric constant as low as 2.49. The dielectric constants decreased gradually with an increase in fluorene loading. The dielectric constant value was not only much lower than non-fluorinated polyimides such as PMDA-ODA (3.16) [127], it was also lower than some of the fluorinated polyimides such as those derived from 3,3, 5,5 -tetrafluoro-4,4 -diaminodiphenylmethane (TFDAM) and dianhydrides (2.73-2.82) [128] and from a,a-fcA(4-amino-3,5-difluorophenyl)phenyl-methane (4FMA) and dianhydrides (2.60-2.83) [129]. Wang et al. [130] prepared fluorinated poly-iinides (3-87 in Table 3.4) by incorporating diisopropyl-substituted fluorene moieties, which led to an improvement in solubility and dielectric properties. The dielectric constant obtained with the... 

A new aromatic diamine monomer with four pendant -CF3 groups was successfully synthesized by a three-step reaction using w(4-fluorophenyl)sulfone and A-bromosuccinimide as starting materials. Then, a series of fluorinated poly(ether sulfone imide)s was conveniently prepared from the diamine and three aromatic dianhydrides (BPDA, BTDA, and ODPA) via one-step solution polycondensation. 

C.-Y. Wang, G. Li, J.-M. Jiang, Synthesis and properties of fluorinated poly(ether ketone imide)s based on a new unsymmetri-cal and concoplanar diamine 3,5-dimethyl-4-(4-amino-2-trifluoromethylphenoxy)-4 -aminobenzophenone. Polymer 50 (7) (2009) 1709-1716. 

Wang et al. prepared a series of novel fluorinated poly(ether ketone amide)s having noncoplanar conformation from an unsymmetrical aromahc diamine (4 -(4"-amino-2"-trifluoromethylphenoxy)-3, 5 -dimethylphenyl)(4- aminophenyl) -methanone and... 

Novel fluorine-containing aromatic poly(azomethine)s are prepared by the reaction of hexafluoroisopropylidene-unit-containing aromatic diamines, 2,2-bis[4-(4-aminophenoxy)phenyl]-l,l,l,3,3,3-hexafluoropropane (17) and 2,2-bis(4-aminophenyl)-l, 1,1,3,3,3-hexafluoropropane (18) with terephthalaldehyde (19) or isophthalaldehyde (20)20 (Scheme 11). 

The cast films ofpoly(azomethine)s are transparent but pale to deep yellow in color. The water contact angles of fluorine-containing poly(azomethine)s films from diamine (17) are 80° for terephthalaldehye (19) and 75° for isophthalalde-hyde (20) as dialdehyde component (Table 9.9).20 These low values of water contact angles are attributed to the lower fluorine content in these polymers. 

Mamyama et al.25 have obtained high-molecular-weight poly(benzoxazole)s by the low-temperature solution polycondensation of A,A 0,0 -tetrais(trimethyl-silyl)-substituted 2,2-bis(3-amino-4-hydroxyphenyl)-l,l,l,3,3,3-hexafluoro-propane (25) with aromatic diacids and subsequent thermal cyclodehydration of the resulting poly(o-hydroxy amide)s in vacuo. In this method, aromatic diamines with low nucleophilicity are activated more positively through the conversion to the /V-silylated diamines, and the nucleophilicity of the fluorine-containing bis(o-aminophenol) can be improved by silylation. 

Many other crosslinking reactions are used in commercial applications. A variety of halogen-containing elastomers are crosslinked by heating with a basic oxide (e.g., MgO or ZnO) and a primary diamine [Labana, 1986 Schmiegel, 1979]. This includes poly(epichlorohydrin) (Sec. 7-2b-6) various co- and terpolymers of fluorinated monomers such as vinylidene fluoride, hexafluoropropene, perfluoro(methyl vinyl ether), and tetrafluoroethylene (Sec. 6-8e) and terpolymers of alkyl acrylate, acrylonitrile, and 2-chloroethyl vinyl ether (Sec. 6-8e). 

Af,Ar,AOV -Tetramethylnaphthalene-l,8-diamine described as Proton Sponge 38 (see Section 1.2) has the ability to act as a fluoride ion donor when its hydrofluoridc is used. Furthermore, it may be used to promote oligomerization reactions of fluorinated alkenes, e.g. 3, and poly-fluoroalkylation reactions with activated perfluoroaromatic compounds, e.g. 4.38... 

Thiazetidine 1,1-dioxides or 3-sultams can be polymerized to high-molecular-weight polysulfonamides.l,2-Thiazetidin-3-one 1,1-dioxides react with aliphatic diamines to give polyamide-poly sulfonamide polymers. Fluorinated 3-keto and 3-imino derivatives were investigated as surface-active agents, and Ai-malonyl derivatives of l,2-thiazetidin-3-one 1,1-dioxide are said to be yellow couplers for color photography. ... 

Sulfur tetrafluoride fluorination of aryl perfluoroalkyl esters provides a route to stable aryl perfluoroalkyl ether compounds (1). By using nitrophenyl esters of perfluoroalkyl-ene and perfluoroalkylene ether dicarboxylic acids, a, w-bis (m-nitrophenoxy) perfluoroalkylene ether intermediates were prepared. The conversion of these products to the corresponding amino and isocyanatophenoxy derivatives is described. Reaction of the diamines with benzophenone-tetracarboxylic dianhydride resulted in formation of poly-imides. Cyclotrimerization of the diisocyanate intermediates formed polyisocyanurates. Both the imide and iso-cyanurate polymers have high thermal, oxidative, and hydrolytic stability. 

Ishii J, Tanaka Y, Hasegawa M. Film properties of polyazomethines (2). poly(imide-azo-methine)s derived from ester-containing dialdehydes, tetracarboxylic dianhydrides, and a fluorinated diamine. High Perform Polym 2010 22(2) 145-58. 

Among various strategies that have been used to synthesize polyimides with lower dielectric constants, the most common approach is to incorporate fluorene, in the form of trifluoromethyl groups, into diamine and dianhydride units that minimize polarizability and increase the free volume [46]. It is well-known that fluorene atom has unique characteristics such as high electronegativity and low electric polarity. These properties give fluorinated polymers (e.g., poly[tetrafluoroethylene]) attractive features such as low water uptake, water and oil repellency, low permittivity, low refractive indices, resistance to wear and abrasion, and thermal and chemical stability. Fluorination is also known to enhance solubility and optical transparency and to lower the moisture absorption of polyimides. Therefore, it is expected that fluorinated polyimides will be widely applied in the electro-optical and semiconductor industries. The polymer series studied was essentially limited mainly to 6F dianhydride because it proved to be the only dianhydride with which many of the fluorinated diamines would form polymer films suitable for physical characterization. 

Banerjee et al. [47] synthesized a diamine monomer, namely, 4,4 -(7w(aminophenoxy)-3,3-trifluoromethyl terphenyl, and furthermore prepared fluorinated polyimides (3-70 to 3-72 in Table 3.4). The Tg of the polyimides depended on the rigidity of the dianhydride unit. The polyimide with PMDA as dianhydride had the highest Tg of 294 °C in the series, with a thermal stability as high as 532 °C in an air atmosphere. The TS of the poly(ether imide) s were in the range 96-112 MPa with an EB in the... 

Yang et al. [121] synthesized a series of colorless poly(ether imide)s from BPADA and fluorinated diamines and investigated the solubility, thermal, mechanical, and optical properties. A representative structure of poly(ether imide) (3-81) is shown in... 

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