Synthesis and characterization of novel polyimide from bis‐(3‐aminophenyl)‐4‐(trifluoromethyl)phenyl phosphine oxide

Abstract

A novel diamine, bis‐(3‐aminophenyl)‐4‐(trifluoromethyl)phenyl phosphine oxide (mDA3FPPO), containing phosphine oxide and fluorine moieties was prepared via the Grignard reaction from an intermediate, 4‐(trifluoromethyl)phenyl diphenyl phosphine oxide, that was synthesized from diphenylphosphinic chloride and 4‐(trifluoromethyl)bromobenzene, followed by nitration and reduction. The monomer was characterized by Fourier transform infrared (FTIR), 1H NMR, 31P NMR, 19F NMR spectroscopies; elemental analysis; melting point measurements; and titration and was used to prepare polyimides with a number of dianhydrides such as pyromellitic dianhydride (PMDA), 5,5′‐[2,2,2‐trifluoro‐1‐(trifluoromethyl)ethyliden]‐bis‐1,3‐isobenzofuranedione (6FDA), 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA), and 4,4′‐oxydiphthalic dianhydride (ODPA). Polyimides were synthesized via a conventional two‐step route; preparation of polyamic acids, followed by solution imidization, and the molecular weight were controlled to 20,000 g/mol. Resulting polyimides were characterized by FTIR, NMR, DSC, and intrinsic viscosity measurements. Refractive‐index, dielectric constant, and adhesive properties were also determined. The properties of polyimides were compared with those of polyimides prepared from 1,1‐bis‐(4‐aminophenyl)‐1‐phenyl‐2,2,2‐trifluoroethane (3FDAm) and bis‐(3‐aminophenyl) phenyl phosphine oxide (mDAPPO). The polyimides prepared from mDA3FPPO provided high glass‐transition temperatures (248–311 °C), good thermal stability, excellent solubility, low birefringence (0.0030–0.0036), low dielectric constants (2.9–3.1), and excellent adhesive properties with Cu foils (107 g/mm). © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3335–3347, 2001

Synthesis and characterization of polyimides from novel 1-(3′,5′-bis(trifluoromethyl)benzene) pyromelliticdianhydride (6FPPMDA)

“…The characterization of 3FPPMDA and its intermediate compounds by FT-IR, 1 H NMR, 19 F NMR, EA and melting point apparatus demonstrated the successful preparation of 3FPPMDA. The overall yield of 3FPPMDA was 49%.…”

“…Tetrahydrofurane (THF, 99.9%, Fisher), toluene (99.9%, Fisher) and p-chlorophenol (99.9%, Aldrich) were vacuum distilled after drying over calcium hydride, while ethylacetate (99.8%, Aldrich) was used without further purification. Bis(3-aminophenyl) 3,4-bis-(trifluoromethyl)phenyl phosphine oxide (m DA6FPPO) [18], bis(3-aminophenyl) 4-(trifluoromethyl)phenyl phosphine oxide (m DA3FPPO) [19], bis(3-aminophenyl) phenyl phosphine oxide (m DAPPO) [30], and 1-bis(4-aminophenyl)-2,2,2-trifluoroethane ( p-3FDAm) [31], as well as PPMDA [32], were synthesized as described in the literature. Phthallic anhydride (PA, 99 þ %) was purchased from Aldrich and sublimed prior to use.…”

“…Novel mono-substituted pyromellitic dianhydrides, 6FPPMDA and 3FPPMDA, were utilized to prepare polyimides in combination with diamines such as bis(3-aminophenyl) 3,4-bis(trifluoromethyl)phenyl phosphine oxide (m DA6FPPO) [18], bis(3-aminophenyl) 4-(trifluoromethyl)phenyl phosphine oxide (m DA3FPPO) [19], bis(3-aminophenyl) phenyl phosphine oxide (m DAPPO) [30], and 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane ( p3FDAm) [31]. In addition, 1-phenyl pyromellitic dianhydride (PPMDA) [32] was also utilized for comparison purposes.…”

“…A dielectric constant as low as 2.3 has been reported via fluorination [3], but at the expense of deteriorated thermal, mechanical and adhesion properties [4]. Thus, it was recently attempted to prepare monomers containing fluorine and phosphine oxide moieties [18,19] since the latter is known to be very effective in improving adhesion as well as fire-resistance [20,21]. In fact, polyimides containing these diamines provided excellent adhesion and solubility, as well as good thermal properties.…”

Synthesis and characterization of polyimides from 4‐(diphenyl phosphine oxide)phenyl pyrromellitic dianhydride

“…This can be achieved by the surface modification of Cu foil by tie-layer coating of Cr, Ti, or polymers, [25][26] or structural modification of polyimides with adhesion promoting groups such as pyridine 27 or phosphine oxide groups. [28][29][30] However, no attempt had been made to adopt all three approaches in preparing polyimides with good solubility, low CTE, and excellent adhesion, until they were prepared from diamine containing adhesion promoting phosphine oxide groups and rigidrod type dinahydrides via solution imidization. [31][32] Unfortunately, the results obtained proved to be slightly inferior for FPC application.…”